r • i , i""" I b-" " , - , Approved for Release: 2018/06/25 C05039582 (b)( 1) (b)(3) 'TO,. S[CRET,----I __ B I F-008..B-00624-I-70-D IS- This document contains 139 pages. Copy ?_::> copies Second Printing COMBINED FINA.L REPORT (Pollution Studies) Study of Treatment Methods of Used Processing Solutions* ..,.- Treatment of Combined ProcessiJ;lg Effluent* .,-- Pilot Testing Study*'* 12 May 1970 Prepared by: date: .3 1'170 Contract EK-1904 * Started under Task 34, Contract EG_400 ** Task 3, Item l(b) of tllis contract. - 1 - TO,. SIE€RET I Approved for Release: 2018/06/25 C05039582 Handl e vi a BYEMAN Control Sys:tem Only C.O --- --- -- -- --- --- (b)( 1) (b)(3)
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This document contains 139 pages.
Copy ~of ?_::> copies
Second Printing
COMBINED FINA.L REPORT (Pollution Studies)
Study of Treatment Methods of Used Processing Solutions* ..,.- Treatment of Combined ProcessiJ;lg Effluent* .,-Pilot Testing Study*'*
12 May 1970
Prepared by:
date: .3 ~+. 1'170
Contract EK-1904
* Started under Task 34, Contract EG_400 ** Task 3, Item l(b) of tllis contract.
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FOREWORD
This report is a· compreh~nsive summary of environmental pollution
studies undertaken at a specific: photographic processing laboratory.
The problem of water pollution asso'ciated with the disposal of
photographic processing wastes ha.s beE;!n considered from both the
ecological and the secu:d ty points of view.
Because this rep0rt refers to a specific facility, it contain:>
data and descriptive information which could identify the facility and
its output volume~ Thus, care must be exercised to avoid compromis-
ing security. Release outside the filcilityis being made at customer
req,uest because of the usefulnes·s of the information to other
installations.
Also, the measured rates, volumes, sizes, and costs stated within
this report are specific in nature and apply to conditions which pre
vailed at the time,of the study.
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SUMMARY
SUBJECT
TABLE OF' CONTENTS
TASKS (from Study Plan)
1. Section IV Task
2. Section V Task
DISCUSSION
3. Description of the Pollution Problem
a. Pollution Magnitudes b. Properties of Processing Efflu~nts c. Photographic Wastewater Effluents· d. Acceptable Wastewater Treatment and Requirements
4. Applicability of Selected Treatment Methods
a. General b. Acidification/Aeration of Fixers c. Biochemical Oxidation d. Chemical Precipitation e. Chlorination f. Evaporation g. Pyrodecomposition h. Ozonation i. Reverse Osmosis, Dialysis/Electrodialysis,
and Ion Exchange
5. Separate versus Combined Treatment
6). Acceptable 'Treatment Methods
a. Biochemical Oxidation b. Evaporation/Concentration c. Pyrodecomposition d. Ozonation e. Reverse Osmosis
PILOT TESTING STUDY
7. Intro.duction
8 Evaporation/Concentration
a. General b. Preliminary Investigation c. Pilot Tests
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TABLE OF CONTENTS (Cont'd.)
Pyrodecomposition
a. Prenco Division of Pickands Mather & Co. b. John Zinc Co. c. Other Incinerators
Solids Waste Disposal
Alkaline Chlorination
a. Test Objective b. Pilot Equipment c. Experimental d. Results
FINAL TREATMENT
12. Final Treatment Facilities
a. General b. Machine Plumbing Changes c. Effluent Collection Tanks d. The Treatment Unit e. Silver-Recovery System
13. Acceptable Treatment Methods
a. Biochemical Oxidation b. Concentration by Evaporation and
Reverse Osmosis c. Incineration
14. Treatment of Toxic Effluents
a. Ferri/Ferro Cyanide Bleach b. Cleaning Solutions c. Fungicide Solutions
BIF-008-B-00624-I-70-
~)age
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60 64 64
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65 65 67 67
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79 79 79
15. Final-Treatment Propos al for BH (Black-and-White) 79 80 16. Final-Treatment for LP (Color)
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TABLE OF CONTENTS (Cant' d. )
CONCLUSIONS'
17. Biochemical-Oxidation
18. Incineration
19. Concentration by Evaporation and Reverse Osmosis
20. Alkaline Chlorination for Color Bleach Wastes
RECOMMENDATIONS FOR BH (Black-and-White)
21. Final Treatment
22. Facility Requirements
23. Limitations, Restrictions and Future Efforts
24. Future Hardware Efforts
25. Future Study Efforts
REFERENCES
.. !'age
81
81
81
82
83
84 84 84 84 84
85 86
APPENDIX A - FINAL REPORT on Acceptable Pollution Standards A-I
APPENDIX B - FINAL REPORT on Study of Pollution Contribution from Processing Activities
APPENDIX C - Tabulated Results of Alkaline Chlorination Pilot Studies
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Properties of Black·-and-Whi te Processing Solutions
Processing Solution Usage and Pollution Magnitude from a Typical Five-Day Blackand-White Processing Mission with Fixer Rejuvenation and Reuse
Properties of the Department Effluent
Make-Up, Composition, and Properties of Synthetic Processing Effluents
Hypochlorination of Type A Processing Effluent
Alkaline Chlorination of Processing Solutions
Chlorine Sources and Chlorination Costs
'Costs of Pollution Abatement Proposals
Pfaudler's Wiped Film Evaporation Pilot Test
Bowen Pilot Test
General Description of Fluid Waste
Incineration Pilot-'rest Results
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SUMMARY
Recommended Treatment
A comparative study of several treatment methcidsshows that bio ..
chemical oxidation is the cheapest, acceptable abatement method for
photographic effluents. All of the effluents from black-and-white af>·
well as color processing, excluding used ferri/ferro cyanide bleache:3,
may be satisfactorily treated, jointly.
For most efficient operation, the biological culture in the activated
siudge or trickling-filter system should be acclimated to a stabilized,
photographic waste. BOD reductions of 80 to 95% were obtained at inrluent
loadings of 30 to 50 lbs of O2 per day per 20,000 gallons of tank volume.
Alternate Treatment Methods
Fluid-waste incineration (pyrodecomposition) is also an acceptable
abatement for used processing solutions. This treatment method requires
the separation of the concentrated waste (developer, de-silvered fixer,
arrest, etc.) at the processor from the wash or rinse process water. Since
the concentration of polluta.rl.ts in the rinse water is low, process water
usually may be sewered, discarded without further treatment, or purified
by reverse osmosis and re-used for photographic purposes, providing that
water conservation is justified economically.
Natural gas or fuel oil must be used as auxiliary fuel to fire the
fluid incinerator up to 1400-2000"F. At these temperatures., the solid
product of oxidation and decomposition is a small amount of a water-soluble
white ash, which may be removed from the stack effluent by a wet-·scrubber
and sewered. The gaseous products of combustion are nearly odorless and
cQlorless.
For installations where water conservation as well as pollution
abatement is a primary objective, evaporat:i,on or concentration of the
concentrated processing effluent is recommended. However, adequate means
must be available for disposal of the residue.
Distillate-to-solid splits of 90% condensate are achievable. with
thin-film evaporator units operating continuously on used photographic
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solutions. The distillate fraction can be s.ewered without further
treatment or purified by reverse osmosis and re-used.
The residue from the evaporator may be a semi-solid or a slurry ..
Disposal may be by incineration in a large, industrial facility, or by
land-fill in an approved disposal site.
Acceptaole treatment methods for effluents containing ferri/ferro
cyanicle from color bleach processing include alkaline chlorination,
pyrodecomposition, and biochemical-oxidation (in a large treatment
facility). The discharge of toxic complex cyanides should be restricted
to an absolute minimum by the acloption of a bleach regeneration and reuse
system.
Final Treatment at BH (Black-and-White Facility)
Adoption of bio-oxidation waste treatment for the facility at BH
is prohibited currently by the large space/volume requirement; namely,
an activated-sludge unit sized to handle the effluent fr0m this in
st!".llation would require a treatment tank in excess of 100,000 gallons.
The alternate treatment method, pyrodecomposition, cannot be recommended
for reasons of operational security: i.e., existing air environmental
cocles require prior approval oy local agencies of all new incinerator
units and authorize on-site inspect:ion, sampling, and testing of stack
effluents.
Because of the above factors, trucking of the used processing solu
tions (excluding rinse water) to a near-by industrial bio-chemical treat
ment facility is recommended as the cheapest, most acceptable abatenlent
meth0d for BH. Rinse water is' to be sewered witho~t treatment.
With this abatement method, the in-house treatment facility will
consist of:
1. Separate waste lines (for used developers,stops, dye-removal
baths, etc.) fr0m each process0r to the collection site and separate
lines (for used-hypo) from each proeessor to the electrolytic silver
recovery area.
2. A double-tank collection unit with transfer or pumping equipment.
3. Sufficient tank-truck equipment so that trips can be made routinely
to disguise the cyclic nature 0f production operations.
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SUBJECT: Study af Treatment Methads af Used Pracessing Salutian; Treatment af Cambined Pracessing Effluent; and Pilat Testing Study ,
TASKS:
1. Sectian IV Task:*
a. Canventianal (Thin Develapers):
(1) Study treatment af develapers with calcium to' remove
sulfite; this study to' cover:
(a) Calcium additian reactian and mixing requirements.
(b) Filtering requirements far remaval af pree:::ipitate.
(c) Salid waste dispasal af filtered precipate.
(2) Canduct a labaratory-level study far remaval af arganic
materials fram develapers.
b. Viscaus Develaper. Canduct studies to' determine:
(1) Quantity (current and future) af viscaus develaper'usedo
(2) Pallutant effects af viscaus develapers. Appearance,
BOD5
and faaming must be cansidered"
(3) Passible treatment methads.
20 Sectian V Task:*
a. Study far immediate needs the fallawing:
(1 ) pH cantral
(2) Remaval af unsaluble campaunds
(3 ) Removal af any calared material
b. Carry aut lang-range data gathering necessary to' produce high
quali ty effluent and passibly pravide reusable water. Distillatian and ~
reverse asmasis to' be cansidered as passible methads of treatment.
DISCUSSION
3. Descriptian af the Palluti<:>n Prablem:
a. Pallutian Magnitudes. Two previaus reparts** have described
and discussed the nature af the pallutian prablem at the BH (Bridgehead)
black-and-white facility. Far purposes af selecting and sizing suitable
*
**
To. tharaughly investigate the pollutian prablem at BH and to' determine a feasible salutian to' this prablem, it was necessary to' extend the scape O.f pallutian studies beyand that specified in these twa tasks.
See References 1 and 2. as Appendices A and B.
These twa reports are included in their entirety
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treatment methods, the salient features of the waste problem are summarized
in Table 1 which is based on these reports containing usage data for 1968.
The following information about chemical usage, oxygen demand, water usage
and rates, 'and used processing solution volumes was derived from Table l.
(1) Chemical Usage. 'rotal chemical usage at BH for black-and
white processing during 1968 was 671,500 Ibs. From chemical. usage estimates
for the MPMP Color Processor*, an additional 20,000 Ibs per year will be
used. Thus, the total chemicals to be discharged via sewers in the near
future will amount to about 691,500 Ibs (about 350 tons) per year.
(2) Oxygen Demand:
(a) The oxygen demand of the chemicals discharged was
determined from chemical usage data and chemical-oxygen-demand (COD) factors
published for the pure chemicals l ,2. The COD will amount to some 207,000 Ibs
per year of O2
(for black-and-white processing), plus an additional 10,000 Ibs
per year oxygen load due to effluent from the MPMP Color Processor. Thus,
total COD load is 217,000 Ibs per year.
(b) Biochemical oxygen demand (BOD) for chemicals found
in photographic effluents is about two thirds (2/3) of the COD load for
these same materials. For black-and-white processing, the annual BOD load
is 136,800 Ibs/year and, for the MPMP Color Processor, the estimate is an
additional 3,200 Ibs; thus total load is 140,000 Ibs per year.
(3) Water Usage and Rates. The total effluent volume of water
consumed for all purposes wi tr:in the department was estimated' from .rater
usage data to be approximately 14.7 million gallons per year. Department
usage rates vary significantly for non-mission and mission rates, for
nightly rates and daily rates, etc. On the average, some 40 to 60,000
gallons of water are used each day at rates varying from 1600 to 4600
gallons per hour.
* A multi-purpose experimental test processor.
1,2 See References.
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. ·Ti3.ble 1
Summary of Department Pollution Magnitude
Chemical Usage
Total Annual Usage (lbs)
OXYSien Demands
Total BOD (lbs/yr)
Total COD (lbs/yr)
Water UsaSie and Rates*
Annual Usage (gal)
Daily Average (gal)
Dept. Usage Rates (gal/hr)
Daily (24 hr avg)
Daily ( 8 hr avg)
Nightly Average
Processing Effluent Volumes
Processing Solutions:
Annual Total (gal)
Annual Average (gal/hr)
Black-and-Whi te Processing·atBH
6'71,500
136,800
206,900
14,700,000
1+0,000
Mission
3,120
3,800
2,250
Maximum Rate Estimated (gal/day)
4119,200
100
3,000
* Includes all water used in the department.
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Estimated from MPMP Color Processor
'Alone
20,000
3,200
10,000
50,000
1,000
Non-Mission
2,730
4,630
1,600
20,000
25
1,000
Dept. Total
691,500
140,000
217,000
14,750,000
41,000
470,000
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(4) Used Processing Solution Volumes:
(a) If all of the used processing solutions (excluding
rinse water) are collected, the annual volume is 470,000 gallons. Most of
this volume (about 450,000 gallons) originates from black-and-white· processing.
(b) The hourly rate of processing solution usage is 100
gal/hr for black-and-white, and an additional 25 gal/hr for coloro The daily
volumes therefore will average abo~G 3000 gallons for both black-and-white
and color. A total of 4000 gal/day is maximum output for the department.
b. Properties of Processing Effluents:
(1) Properties:
(a) The major' polluting. effects from the discharge of
photographic processing solutions are: high total-dissolved-solids content,
and high chemical and biochemical oxygen demand (COD and BOD5
). In addition,
effluents containing used photographic wastes re"luire special treatment to
meet waste-water disposal requirements established for:
1. pH
2. Alkalinity and/or acidity
1. Dissolved solids
4. Phosphates
L.. Iron
6. Cyanides (and complex cyanides)
I. Phenols (and phenol~c by-produ'cts)
8. Other miscellaneous organics
(b) Photographic solutions for black-and-white processing
vary greatly in their pollution characteristics and in the relative volUmes
consumed. Both factors must be considered in selection of a suitable abate-
ment method.
(b)( 1 ) (b)(3)
(c) Properties of black-and-white processing solutions are
sUJlIDlarized in Table 2. As can be seen from this table~ fixer soluti.ons are
exceptionally high in solute content, i.e., 30% by wt; while developers, stop
baths, and dye removal baths contain only approximately 10% solutes. Developers
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and dye-removal baths are high in alkalinity; on the other hand, fixers ahd
stop baths are high in acidity. All processing solutions, except tb;e dye
removal and Photo Flo baths, are high in oxygen demand (COD and BOD5
).
Furthermore, rinse water from black--and-whi te pr0cessihg contains about
0.1 gil dissolved solids, some halides ('V 100 ppm), and has a low oxygen
demand (COD 'V 75 ppm, BOD 'V 45 ppm) '. The pH generally ranges from 6-8 and
the water is clear and colorless.
(2) Usage Rates:
(a) Used developers comprise the largest volume of effluent
discharged from this installation. If rinse waters are excluded, developers
* make up 70 to 85% of the volumes of processing solutions mixed and sewered.
(b) When usage rates as well as the pollution load are
considered, it is found that about ~51% of the total dissolved solids origi
nate from developer solutions, 44% from fixers, and only 5% from stop and
dye-removal baths. Similarly, over 90% of the oxygen demand (both COD and
BOD) of processing effluents stems from the developers and fixers. Thus,
segregation and treatment of the used developer and fixer solutions will lower
most pollution parameters by 90% or more. If the relatively small quantities
of step and dye-removal'baths are also treated, excluding only the rinse
water, about 99% of the pollution from photographic processing could be
removed. (See Tables 2 and 30)
c. Photographic Wastewater Effluents:
" (1) 'For abatement pur:bloses, two types of waste water "Till be
considered for treatment: the concentrated processing effluent, ineluding
all of the used processing solutions, but excluding all process water; 6r
the diluted processing effluent, which combines the used processing solu
tions with all of the water us ed by the department. Both types of effluents
will be considered. in the selection of suitable abatement methods.
* Percentage depends upcm whether or not hypo is rejuvenated and, reused.
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Table 2
Properties of Black-and--White Processing Solutions
(b) Analysis of the spray cut-off sample from the sump
gave the following data:
1. Color: Clear, colorless
£. pH at 10F: 7.72
3. Halides: 0.05 gil as KBr 0.06 gil as NaCl
~. COD: 75 ppm
(c) , An estimate of the concentration of developer and.
developer constituents in the proc'=ssing effluent was made from the above
data. Each gallon of effluent was estimated to contain about 9 I!ll of
developer; i. e., a dilution ratio of about 440 to 1. 0 ~ . At this dilution,
* the concentration of photographic "flags" from a typical developer solution
is as follows:
1. Sodium sulfite: Less than 0.10 gil
2. Phenidon: Less than 0.01 gil
1· HQ: Less than 0.01 gil
4. Thickening agent: Less than 0.03 gil
2· Bromi,des (e.g. , KBr) : Less than 0.05 gil
* Constituents or characteristics indicative of processing. '
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(d) These concentrations of photographic "flags" in
the processing effluent are not detectable by the usual analytical.methods
applied to wastewater 3 • Thus, process wastewat~r from deep-tank or spray
Gut-off rinses can be sewered without jeopardizing the operational security
of this department .•
d. Acceptable Wastewater Treatment and Resuirements:
(1) City Sewer Code Limitations:
(a) To continue the discharge of effluents into :3 ewer ,
the City Sewer Code restrictions 4 must be met. Since the department effluent
changes drastically in volume and properties, slugging roestrictions of the
City Sewer Code apply to the effluent. Thus a suitable pollution ruJatement
method must eliminate "slugging" as defined by the City Sewer Code .
(b) The City Commissioner 0f Public Works might also rule
that certain properties of the effluent 'are "unusual" or might "have an
adverse effect" upon the sewer system or treatment process. Effluents with
a high BOD, COD, solids content, or high organic level might be the cause
for further investigation.
(c) It should be noted that at present there is no actual,
defined violation of the City Sewer Use Code at this facility, with the
possible exception of pH. Thus, the effluent of this department is essenti
ally acceptable under existing sewer code limitations. With a sui table
collection and storage system equipped with automatic pH' adjustment equipment,
the department effluent could be se'wered if it was not required also to
maintain operation security.
3,4 See References.
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(2) Acceptable Security Standards:
(a) To maintain operational security, pollution centrol
must effectively accomplish the following objectives:
1. Maintain a strictly acceptable waste effluent
which will reduce or eliminate the need for a detailed examination of the
efflu~nt by an outside agency •
2. Restrict or eliminate photographic flags; i.e.,
constituents or characteristics indicative ef processing.
1. Disproportionalize acceptable constituents of
.. our effluent so that the true magnitude of processing operations cannot be
ascertained from the materials and quantities discharged.
4. Disguise the cyclic characteristics of the
industrial effluent.
(b) Specific implications for an acceptable pollution
control system are given by Table 13 in Appendix A. By adopting these
standards for acceptable pollution control, the effluent of this department
will have properties similar to those of city sewage; thus, its properties
would not be "unusual" nor harmful to the City Sewer System or treatment
plant.
(3) Other Limitations. The physical size requirement~3 of any
proposed treatment methed also must be considered in the feasi bilh;y study.
Locating a suitable treatment center at this facility could involve serious
restrictions in physical dimensions; e.g., in weight, height, area, volume,
etc. Also, since costs for pollution control will be shared. with the
customer, equipment costs and operational costs including labor required, /
must be considered in selecting an applicable abatement system.
4. Ap;plicability of Selected 'rreatment Methods:
a. General. A literature search was made of established abatement
methods that might be applicable to some of the used processing solutions.
Both chemical and physical methods 'were studied. The applicability of each
treatment was determined from published evaluations of the method when
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treating industrial wastes which have properties similar to those o:f used
processing effluents. The following sections describe several methqds
which have been proposed for specific types of photographic effluents.
b. Acidification/Aeration of Fixers:
(1) Description. The addition of an acid to a thiosulfate
solution decomposes the thiosulfate to sulfur and sulfur dioxide. f3ulfi tes,
as well as thiosulfates, are subject to decomposition with strong acids.
This method of separately treating fixer solutions has been studied
by other investigators who arrived at the following conclusions:
(a) Acidification, alone, is not sufficient to completely
decompose all the thiosulfate and sulfite ions.
(b) Acidification with either hydrochloric or sulfuric
.acid, followed by aeration, will decompose about 90% of the sulfite and
thiosulfate in a typical fixer bath.
(c) The method substi t-qtes a degree o.f air pollution
for water pollution becaus.e sulfur dioxide is liberated.
(d) Chemical costs (for sulfuric acid) are estimated
at $0.017/1b for destruction of sodium sulfite and $0.022/1b for sodium
hypo; or, about $0.04 per gallon of fixer, not including capital, air, and
operational costs.
(2) Costs:
(a) The cost of sulfuric acid to adequately treat 62,500
liters (1700 gallons) of dye-removal bath would be $250 per year.
(b) The cost of comme~cial-grade sulfuric acid to treat
and partially remove BOD/COD caused by sulfites and thiosulfates in the
combined effluent (excluding rinse water) would be $8,000 to $10,000 per I
year.
(c) Capital items required for the acidification!
aeration treatment would cost about $10,000 as shown below:
l. Two 300O-gallon collection tanks with mixer $ 6,000
2. pH control
}. Acid storage and dispenser
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Approved for Release: 2018/06/25 C05039582
1,000
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(3) Conclusions:
(a) Acidification/aeration best applies in the treatment
of the sulfite dye-removal bath.
(b) This method ,fill only partialJj treat fixer, developer,
or a combined processing effluent. A reduction of 45 to 50% in BOD/COD will
be gained at the expense of air pol-lution (sulfur dioxide). - A follow-up
treatment, such as alkaline chlorination, will then be required to further
reduce oxygen demand to an acceptable level.
co Biochemical Oxidation:
(1) General:
(a) The secondary treatment of photographic effluents by
biological degradation has been evaluated for both co10r and black-and-white
process wastes. Using re"';'cycled sludges containing micro-organisms accli
mated to photographic wastes, the following results have been observed: 5
1. BOD values are reduced by about 90% and COD
by 65%.
2. Photographic effluents are usually toxic to the
micro-organisms, unless first acclimated.
1. Ammonium ion is not affected or reduced by this 10
treatment.
4. Some organics, especially aromatic compOlmds, are
not degraded by this treatment; notably, phenol derivatives 7.
L. Photographic waste treated by this method will
give an effluent suitable for discharge into a City Sewer without further
treatment.
(b) In biological oxidation systems, the design determines -
the efficiency and size requirements. If enough land is available, la.goons
or oxidation-ponds can be used to treat wastes at BOD loadings ranging from
50-100 Ibs per acre of surface per day. Lagoons are able to absorb 400-500%
overloads for short times without a.dverse affects.
5 , 7 See References.
* A second anaerobic treatment tank is required if ammonia/ammonium ion content is to be lowered.
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(c) When land is not available, other approaches are
used to improve the efficiency of biolQgical oxidation systems. Trickling
filter beds achieve 1 to 5 Ibs/day per cubic yard of stone; efficiency of
this method ranges from 35 to 85%. Plastic filter media are also available
at about double the surface area/volume ratio. A two-stage trickling
filter system is generally 80 to 95% efficient in reducing BOn6• '
(d) Other methods of reducing the volume/space require
ments are to recirculate a portion of the sludge containing the micro
organisms and to increase the oxygen content by aeration of the waste.
Thus, in typical activated-sludge units, BOD loads of 15 to 150 Ibs per
1000 cu ft of tank volume are handled in r,etention times of 4 to 24 hours.
If oxygen is used instead of air, the tank volume may generally be reduced
30-50%; however, operating costs will actually double.
(2) Size of Unit:
(a) Since land or space for a biological treatment
facility will be at a premium, only the trickling-filter and activated
sludge methods can be considered. Using a plastic trickling-filter media,
the tank volume required would be.in the range of 50 to 70 cu yds. The
most ideal trickling-filter system would be comprised of two tanks con
nected in series, each about 10-ft high and 10-ft in diameter. The
largest reduction in BOD would take place in the first tank; the second
tank would not be required, if the wastewater was to be sewered. If the
effluent was to be discarded in a stream, river, or lake, the' second tank
would 'eventually be required to .meet the Water Quality Classification for
the body of water •
(b) The effect of. "slugging" on the biochemical system
can best be minimized by using two storage-tank systems for the effluents.
The concentrated processing solutions should be collected and stored in a
5000-gallon mix tank and fed at a constant rate to the system. A regulated
amount of the other, more dilute process water would also be metered. to the
aeration tank.
6 See References.
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(3) Photographic Flags:
(a) Some organics are only partly oxidized or destroyed
by a biological system. Hydroquinone, for example, is oxidized to cluinone,
which' resists further biodegradation 7• Ferri/ferro cyanide wastes ,> from
color bleaches are not adequately removed by biochemical means, although
they can be mixed without any damaging effects upon an acclimated bio-·
logical system. The effluent from biological treatment will therefore
contain some organics which could be flags or indicators of photographic
processing.
(b) Ammonium ion generally is not removed by conventional
acti vated-sludge (AS) systems 9. To remove ammonium, a second treatment tank
is used to provide an anaerobic treatment. Since the effluent will be
sewered, the small concentration of ammonium ion originating from the treated
processing effluent will not be discernible or distinguishable from that
already present in tne sewer from domestic sources.
(c) The unusually high sulfate content previously present
in the effluent will be lowered substantially when hypo rejuvenation and re-. ,
use is fully operational. A lime post-treatment to remove sulfate ions
(from the oxidation of sulfite and thiosulfate) should not be required if
the effluent is sewered. For discharge to a stream, however, a lime treat
ment is recommended, followed by chlorination. The removal of sulfate by
lime precipitation would prevent po~;sible disclosure of the magnitude of
processing operations by monitoring the sulfate content and volume of waste-
water.
7 ,,9 See References.
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(d) The proper operation of a biochemical treatment
plant would require:
1. Control of temperature; i. e., steam heating
coils' for p'roper operation in the w'inter months.
2. Laboratory support to monitor pH, BOD, COD,
sludge build-up, etc.
3. Chlorination of effluent to kill bacteria
or remove traces of photographic flags.
4. Annual sludge disposal in which the removal
of sludge from the system would require a weekend shut-down. The solids
removed could be trucked to a land fill site or incinerated.
(4) Costs:
(a) To reduce the BOD in this effluent by 140,000 Ibs
02 per year (385 Ibs/day), an AS system having a capacity of 75,000 to
100,000 gallons would be required. The dimensions of the AS unit would
be approximately 24-·ft wide, 50-ft long, and 10-ft high; the initial cost
* would be $75,000 to $100,000 •
(b) Annual operating costs would be $15,000 for utilities,
power, heat, etc.; plus, labor (one,-half man) estimated at $10,000. The
estimated cost of treating all processing wastes from this department would
therefore be about $25,000 per year or about $0.015 per liter ($0.0:)5 per
gallon) of used processing solution.
*
NOTE: All of the processing wastewater would
be treated, including rinse water; this
estimate is based on the combined volwnes'
of used developer, fixer, arrest and dye
removal bath.
This estimate is based upon the performance of a pilot unit (12 ft x 10 ft x 25 ft) treating 20,000 gallons of photographic wastes per day. The BOD is reduced from about 200 ppm to 20 ppm which is equivalent to 36 Ibs BOD per day.
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(5) Conclusions:
(a) A single aeration tank AS unit or a trickling
filter tank would adequately pretreat the department wastewater for dis
charge to t'he sewer.'
(b) Size requirements would probably prohibit adoption
of this treatment method.
d. Chemical Precipitation:
(1) General:
(a) The chemical treatment of photographic wastes has
been considered by several authors. Mohanrao et a19 cited the effects
of alum, ferric chloride, ferrous sulfate" lime and their combinations
on composite photographic wastes. Lime and alum were found to have some
abatement effects; i.e., reduction in color, COD, and dissolved solids
content.
(b) . EustancelO
described methods and equipment for
chemical abatement by precipitation.. Facilities for flocculation, sludge
removal, and vacuum drying of solids are required.
(c) A study was made of the solubility data of compounds
which could be removed from photographic wastes by chemical means; from
this study, it was concluded that:
1. The addition of lime followed by floccula'tion
should significantly reduce total dissolved solids. Ions precipitated
would include phosphates, carbonates, borates, and ferri/ferro cyanide
complexes.
2. Some "toxic" constituents are reduced; i.e.,
some organics are adsorbed, or absorbed by the precipitate, and ammonium
content is reduced.
1. The color of the effluent is appreciably :ceduced.
4. Chemical treatment with lime and/or alum is not
adequate for removing those constituents of photographic wastes which have
a high oxygen demand.
9,10 See References.
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Handle :via BYEMAH Control System Only
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(2) Heavy Me.tal Precipitation:
(a.) The sulfi tes and thiosulfates of most commercial
coagulants ,or flocculents are too soluble to remov:e appreciable am01'illts
of these ions. Only the lead and barium salts of these cations are in
soluble. However, since both lead and barium are highly toxic, meticulous . control would be required to prevent these cations from being used in
excess amounts.
(b) To reduce the BOD/COD load caused by sulfite (803
=)
and thiosulfate (82°3=) by chemical precipitation, two methods may l)e
proposed:
1. Precipi tation with lead or barium ions, or
2. Oxidation of 8°3- and 82°
3- to sulfate (S04 =) ,
followed by precipitation with lime,.
(c) Precipitation of sulfites and thiosulfates with
lead or barium would remove 45 to 50% of the BOD/COD load. The use of the
cheaper chemical (barium chloride) 'il'Ould require 2 Ibs of BaC12 • 2H20 for
every pound of hypo or sodium sulfii;e. Two pounds of solids (Ba804
) would
be produced for each pound 0f hypo or sodium sulfite treated. The barium
sulfate could be used for other purposes; e.g., sizing, baryta, etc.
(3) Lime Precipi tatior~:
(a) For security reasons, it might be desirable to remove
from the oxidized effluent as much of the sulfate and chloride as possible
after hypochlorination, ozonation ,'biochemical treatment, or alkaline chl0ri
nation. Precipitati0n with lime (CaO) removes most, of the sulfate as calcium
sulfate (Ca804 .2H20).
(b) The following equations give the approximate amount
of lime required and the weight ratios of solids precipitated per unit
weight of hypo or sodium sulfate treated:
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°2 Na2S203.5H20------,J .... 2S04 (Hypo)
= +
(1) --------. (0.77) + (8.45) ----+-(1.38)
= Na2S03
+
(1)-----;..,.-( 0 0 76) + (0.445 )----to-( 1036)
(I)
(2 )
For each pound of hypo (Na2S203.5H20) or sodium sulfite, about 0.45 Ib of
lime will be required to adequately precipitate the sulfate ion. Since
there will be some moisture in the precipitated solids, there will -be about
1. 5 Ibs of solids per pound o-f hypo or sulfite treated.
(4) Costs:
(a) The chemical costs for precipitation with ba~ium
chloride have been estimated as follows:
1. For treating Na2S03
: $0.20 per
2. For treating Na2S203·5H20 ("Hypo") : $0.20 per
1· For treating a typical fixer: $0.08 to
Ib
Ib
0.10 per gallon
Annual cost for barium chloride to remove 45 to 50% of the BOD/COD load
by chemical precipitation would be about $31,000. (Cost of BaC12 .2H20 = $200/ton) •
(b) The cpemical costs for precipitating sulfates with
lime are as follows:
1. Lime:
2. Each pound of sodium sulfite or hypo oxidized to sulfite:
(c) Capital costs would be:
$20/ton
$0.005 per Ib
1. Two 3000-gallon tanks $ 6,000
2. pH controller 1,000
3. Lime storage, mix tank and dispenser 3,000
4. Vacuum or drum filter 0_5 ,000
_. 27 -
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Approved for Release: 2018/06/25 C05039582
Total $15,000
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(d) Cost to operate the system:
1. One ~an half-time:
2. Utilities:
$10,000
2,000
Total $12,000 per year
(e) The chemical costs for hypo chlorination and chemical
precipitation with calcium hypochlorite (HTH) are discussed in paragraph
4.e.(5)(c) on page 36.
(5) Conclusions:
(a) No known single method or combination of chemical
treatment methods is adequate for treating processing wastes and maintaining
operational security.
(b) Chemical costs for barium or lead salts are high in
proportion to the limited reduction in BOD/COD obtained by precipitation
with a heavy metal.
(c) With no preliminary oxidation, treating wastewater
of this department with lime will give only a 10 to 15% reduction in BOD/COD
and a 30 to 40% decrease in total salt content. The effluent from this
abatement step will still contain numerous "flags" of photographic :~rocessing;
thus post-treatment will be necessary.
(d) The oxidation and precipitation could be carried out
simultaneously with a bleaching agent such as calcium hypochlorite (HTH).
Estimates indicate that 30 to 60% of the BOD/COD could be removed by treat
ment with HTH.
(e) About 1 Ib of bleaching powder (HTH, Maxoclor, or
70% available, C12 as calcium hypochlorite) would be required to treat each
liter of effluent from a typical processor.
(f) If the sulfite and thiosulfate are first oxidized
to the sulfate, then precipitation 'with lime will be adequate to remove
dissolved solids. Oxidation of the effluent may be by chlorination or by
biochemical means (activated sludge tank, trickle filter, lagoons, etc).
Subsequent treatment with lime would produce an effluent having a solids
content of about 2000 ppm and having practica+ly no oxygen demand'.
28 -
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(g) Treatment of the combined effluent with lime would
require 0.45 Ib of slaked lime for every pound of hypo or sodium sulfite
oxidized by treatment methods. In both instances, 1. 5 Ibs of solids could
be separated for lan'd diE?posa1.
(h) A disposal area for solids would be required.. About
two pounds of solids would have to be dumped for each pound ·of solute removed
from the processing effluent.
e. Chlorination:
(1) General:
(a) Literature l l.-14 on chlorination of industrial wastes
indicates that alkaline chlorinati,on should be a complete treatment for all
used photographic solutions; this method of treatment:
1. Reduces BOD/COD load by oxidation of sul:fi te,
thiosulfate, and organics; examples are:·
H3 C COOH + 02
(Acetic acid)
20 Destroys toxic materials; an exampl.e is:
1. Chemically changes/removes processing flags;
(2 )
(4 )
two examples are:
(' -3 (0)
Fe GN) 6 -Cl-2-:"':+:":-N-a--=-0 H----:JJPIJP Fe ( OH ) 3 ~ + 6 CO 2 t
+ .3N2 t + H20 + NaCl
11-14 See References.
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4. Oxidizes organics; an example is:
(b) There are tvto methods 0f applying chlorine. Chlorine
gas may be injected into an effluent stream from a liquified chlorine source,
or by hypochlorination. Hypochlorinati0n can be achieved by treating the
wastewater with a solution of sodi~~ hypochlorite (15% by wt NaOC1) or with
a solid chlorine-bleach, such ascalctum hypochlorite (HTH) which generally
contains about 70% by wt available chlorine.
(c) Modern equipment for applying chlorine gas is rela
tively simple, inexpensive, and s-afe. The chlorine source and storage may
be distant from the chlorination site. The transfer of the chlorine from the
supply to the injection eQuipment may be made entirely in the gaseous phase
via supply lines under a partial vacuum.
(d) Theoretically, for each pound of chemical 0X:f.gen
demand removed from the effluent, at least 4.43 Ibs of gaseous or "available"
chlorine are reQuired. However, the oxidation of some processing pollutants
requires only small amounts of chlorine and caustic. For example, to oxidize
1 Ib of sodium sulfite to sulfate reQuires 0.53 Ib of chlorine plus an equal
weight of caustic*. To oxidize 1 Ib of s0dium thiosulfate, 1.10 Ibs of
chlorine and 1. 6 Ibs of caustic are reQuired. The complete oxidation of
many compounds necessitates that the chlorination take place in an alkaline
solution (pH = 10 to 12). For many organics, the weight ratio of caustic to
chlorine is greater than 2 or 3 to one.
(e) Alkaline chlorination will thus introduce at least
9 Ihs of dissolved solids (sodium chloride, etc.) for each pound of COD
removed. Post-treatment of the chlorinated effl~ent with lime and/or sulfuric
acid could be used to lower the pH and to remove some of the total dissolved
solids.
* See eQuation (1)" on previous page
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(2) Hypochlorination of Fixers:
(a) Experimenta*. In the laboratory, 50cc of used de
silvered (sodium thiosulfate) fixer were treated with 5-gram additions of
calcium hy:pochlorite (HTH - 70% available chlorine). The tan, voluminous,
fine precipitate was filtered and the filtrate again treated with a 5-gram
portion of HTH. After four such treatments, the solids were white in color
and no further chlorination occurred. The filtrate was slightly green in
color and highly acidic (pH 'V 1. 0). The filtrate was then titrated with a
lime slurry until alkaline. Additional white solids were formed and these
were allowed to settle. The supernatent liquid was then clear and color
less.
(b) Results:
1. At the end of the fourth treatment with HTH
(20 grams), a test for thiosulfate was negative.
2. The COD of the filtrate was found to be
10,000 ppm.
1. After treatment with lime, the total solids
content of the filtrate measured about 17 g/1.
(c) Conclusions:
1. The reduction of BOD/COD in a typical (sodium)
fixer solution was 85% complete. Treatment with calcium hypochlorite
oxidized only the sulfite and thiosulfate.
2. Acetic acid and other organic sources of BOD
or COD were not removed by chlorine under these acidic conditions by
chlorination.
3. The use of calcium hypochlorite caused preci
pitation of some of the sulfates (formed by chlorination of sulfite and
thiosulfate) as'CaS04' reducing the dissolved solids content of the
effluent.
4. Considerable heat is liberated in th!'O process.
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(3) HyPochlorination of Bleach:
(a) E.xperimentaJ~. Exactly 10cc of a used bleach solu
tion was diluted to about 50cc with water and then treated with 10 grams
of HTH. No reaction was apparent; i.e., no color changes, heating, gasing,
etc. A second sample of diluted bleach was made alkaline (pH~ 10) with
NaOH and then similarly treated with 10 grams of HTH. Some lessening in
color and heating occurred. After 1 hour, the pH was again adjusted to 10
or greater and an additional 10 grams of HTH was added. I (b) Results and Conclusion. The fil tr.ates from ·bleach
samples treated with HTH consistently gave a positive tesk for ferricyanide.
The de·struction of ferri/ferro bleach by hypochlorination is not feasible.
(4) Hypochlorination of Photographic Syntheltic Effluents:
'(a) Preparation of, Two Synthetic Efflu'ents. To study
treatment methods for the combination of processing SOlut!ions; developers,
arrests, dye-removal baths, and fixer processing SOlutionis were com'bined in
the proper proportions to obtain two types of concentrateld photogra:phic -- I synthetic effluents. These two concentrated effluents .are similar, except
that Type A Effluent contained a used, desilvered sodium ~hiosulfate (F-6)
fixer, whereas, an ammonium thiosulfate fixer (KRF-type) was added :in
Type B Effluent. Selection of the types and the·relative volumes of each
processing solution was based upon usage data during a typical mission.
Table 5 summarizes the make-up, composition, and gives some of the Ilhysical
and chemical properties of these effluents.
(b) Experimental.. One hundred mls of a concentrated
synthetic effluent consisting of the proper ratio of fresh develope:r, used,
desil vered fixer, arrest, and dye-removal baths (see Table 5) were diluted
to about 1 liter and treated with HTH. Variables in these experiments
included the' adjustment of pH with caustic solution, repeated addit:Lons
of HTH, heating, and allowing the treated samples to stand overnight.
COD measurements were made on the clear filtrates. Table 5a summarizes
the variables and the results.
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Table 5
Make-Up, Composition, and Properties of Synthetic Processing Ef~luents
Make-Up
Processirt~ Solution
Developer Developer Arrest Dye-Removal Bath Dye-Removal Bath Fixer Type
Specific Gravity (at 70F)' pH (at 70F) Viscosity (Brookfield at 70F) Freezing Point Ash (Incinerated) Color Oxygeri Demand (g O2 per liter):
COD (Theoretical) COD (Observed) BOD (Observed)
Chlorine Demand (g C12 per liter):
Theoretical
Type A
1.062 6.91 500 cps 26F 6.75% Amber
48.8 47.0 36.3
215
Type A Effluent: F -6 (Sodi urn hypo); Type B Effluent:
-- 33 -
TOP SECRET/ ~ ___ ...J
Approved for Release: 2018/06/25 C05039582
.'!TIle B
1.054 6.87 700 cps 261" 6.75% Amber
79 .. 2 53 .. 0 42 .. 0
350
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Table 5A
Hypochlorination of Type A Processing Effluent* . Sodium Hydroxide
Temp pH Added Chlorine Source COD Test No ./Sample i.!:.L (at 70F) (grams) and . Amount ~ Notes --
ll. Type A - 100 mls 80-90 6-8 0.0 Og HTH** 4,400 Before dilution COD is approximately 44,000 ppm
a. Type A - 100 mls 80-90 7.90 0 25g HTH 3,096 b. Type A - 100 mls 80-90 8.22 0 50g HTH 2,836
12. Type A - 100 mls 80-90 6-8 0 Og HTH 4,400 a. Type A - 100 mls 80-90 12-13 10 25g HTH 2,568 b. Type A - 100 mls 80-90 12-13 20 75g HTH 2,530
13~ Type A - 100 mls 150-160 6-8 0 Og HTH 4,400 a. Type A - 100 mls 150-160 61-8 0 50g HTH 2.700
w b. Type A - 100 mls 150-160 12.0 10 50g HTH 2,700 .j::"""
Type A - 100 mls 150-160 11.8 20 SOg HTH 2,400 c. d. Type A - 100 mls 150-160 12.3 30 50g HTH 2.400 e. Type A 100 mls 150-160 12.1 20 75g HTH 2,350 f. Type A - 100 mls 150-160 11.8 20 100g HTH 2,368
14. Type A - 100 mls 120-160 6-8 0 Og HTH 4,400 a. Type A - 100 mls 120-160 12-13 10 25g HTH 2,648 Let stand for 5 hours b. Type A - 100 mls 120-160 12.45 20 50g HTH 1,890
15. Type A - 100 mls 80-90 6-8 0 Occ Bleach*** 4,400 tD
a. Type A ':'" 100 mls 80-90 13.4 35 150cc Bleach 2,896 Let stand for 30 minutes "T1 I
b. Type A - 100 mls 150-160 13.5 35 150cc Bleach 2,900 Let stand for 30 minutes 0 0
g~ 00 I
:> :> tel .-+0. I d CD fl nn ml",)
0 * Before hypochlorination, the sa.>nple -r.·ras diluted t8 1000 mls. (b)( 1 )
,--, ., \-'- ........ J.~ .. -'- oJ I 0\ en -. I\) '< I»
** (70% available C12
) '" Commercial grade of calcium hypochlorite (b)(3) +:-'-+tD I ~ -<
(15% by wt NaOC1) H
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(c) Results:
1. The simple bleaching of a combined photographic
effluent with calcium hypochlorite at room ambient temperature and without
caustic additions reduced COD by about 64%. The addition of caust:Lc to
adjust the pH between 12 and 13 increased the chlorination slightly, but
half (58%) of the COD still remained (2530 ppm).
2. When the hypochlorination was carried out at
150 to 16oF, the chlorination was more complete (53%), leaving an effluent
with a COD of 2350 ppm. After standing for 5 hours at 120 to 16oF, about
60% of the COD was removed, leaving an effluent having a COD of ab~mt
1890 ppm.
1. Hypochlorination with a 15% solution of sodium
hypochlorite did not achieve more than a 35% reducion in COD, leav:i..ng an
effluent with an oxygen demand of about 2900 ppm.
(5) Alkaline Chlorination of Processing Solutions:
(a) EX1Perimenta1. A small chlorinator was assembled
from a 250-ml glass measuring cylinder and a sintered-glass bubbler tube.
A I-lb lecture-bottle cylinder of chlorine was used as the gas SOill~ce. A
known volume of the used processing solution was diluted (as required) and
added to the measuring cylinder. 'rhe pH was raised to 10 - 12 by adding
caustic solution (50% by wtNaOH). Chlorine gas was introduced ai., a con
stant rate (0.5 l/min = 1.0 g/min) for periods up to an hour. The temper
ature was monitored to determine rate of oxidation. The pH was checked
periodically and caustic added to maintain a high degree of alkalinity
(pH 'V 10 to 13). Table 6 lists some of the test details for processing
solutions discussed below.
1. Fixer:
a. A typical sodium thiosulfate fixer, ,having
a theoretical COD of 105 grams of 02 per liter of fixer, has a (theoretical)
chlorine demand of 465 grams of available chlorine (Chlorine Demand =
4.43 x Oxygen Demand, theoretically). Thus, to completely reduce the COD
-- 35 -
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t Approved for Release: 2018/06/25 C05039582
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Table 6
Alkaline Chlorination of Processing Solutions
Chlorine Time Caustic Solution Temperature Rate Weight COD*
a. 15 45 0.5 15 8,600 b. 30 +50 114 65 0.5 30 5,400 c. 45 '\,60 0.5 45 3,500
12. Developer: 100 mls 0 100 76 25 0.5 0 [16,000)
a. 15 55 0.5 15 9,000 b. 30 +25 95 60 0.5 30 <3,500 c. 45 65 0.5 45 3,200 a:J
[ro,oooJ ."
5 . Sodium Fixer: 100 mls 0 50 38 22 0.5 0 I 0
g; 0
a. 5 56 0.5 5 ex> :> :> I r+Q.
b. 76 td ., - 10 +50 50 0.5 10 o CD I '< c. 30 +50 114 30 0·5 30 . 4,500 0
~ \.i.i-' 0 '<. II> (cooled) 0\ II> f\) r+a:J
d. 45 +50 152 28 0.5 45 5,000 -I=""' ~ -< I o~ H
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* COD values in brackets [ ] are theoretical values of the diluted sample ;. (b)( 1 ) all others are observed values on the chlorinated samples. (b)(3)
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of a 100-ml sample of fixer, about 46.5 grams of chlorine are required.
In addition, about 50 grams of sodium hydroxide would be theoretica~ly
needed to maintain the alkalinity level during complete chlorination.
b. In the laboratory experiment (Test Nb. 5;
see Table 6), the temperature began to drop significantly after chlorina
tion had proceeded for 20 minutes, indicating that the rate of oxidation
was decreasing. After 30 minutes of chlorination (30 grams of C12 )" the
effluent had the lowest COD; i. e., 4500 ppm * . c. Taking into account the dilution factor,
about 90% of the COD was removed in less than 30 minutes by 60 grams
(or less) of chlorine and. 75 grams of NaOH.
2. Viscous Developer:
a. In Tests No. 10 and 12 (see Table 6)"
100 mls of a typical viscous developer were chlorinated. After only
15 minutes, the COD of the effluent reached a minimum. Continued
chlorination did not reduce the COD below 3200 ppm.
b. The theoretical COD of this developer'
solution was 50.4 grams of O2
per liter. The chlorine demand of 100 mls
was therefore 22.5 grams of C12 • After 15 minutes of chlorination, the
COD therefore was reduced by about 85%.
1. Stop Batl~:
a. A 100-ml ·sample of arrest bath was diluted
with an equal volume of caustic solution and the mixture chlorinated for
one hour. The COD values were g600 ppm after 15 minutes (and 15 grams of
C12
); 5400 ppm after 30 minutes (and 30 grams of C12 ); and 3500 ppm after
45 minutes (and 60 grams of C12 ). The theoretical COD is 38.4 grams of
O2
or 170 grams of C12 per liter.
* These COD values were determined by the standard dichromate method. They are not corrected for chloride content; thus, these values may be 1 to 5% high. For this reason, continued ch10rination of samples usually gave slightly higher values of COD.
- 37 -
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b. After twice the amoUY).t of chlorine had been
added, the COD was reduced by only 55%; after four times the requil;ed
chlorine, 28.5% of the COD remained; EjIld after 5.3 times the theoretical
chlorine consumption, about 18% of the initial COD stlll remained.
(b) Summary:
1. The sto:ichiometric ratios of the "following
equations best. describe the alkaline chlorination of the major constituents
2. For example, for every pound of hypo chlorinated,
1.15 Ibs of chlorine and 1.6 Ibs of sodium hydroxide ar.e. required and about
1015 Ibs of sodium sulfate and loSe Ibs of salt (NaCl) are produced.
(c) Costs:
1. The chemical costs for alkaline chlorination are
dependent upon: the volume and COD of the effluent; the source of the
chlorine; and the degree of oxid?-tion desired or required for acceptable
treatment.
2. Tables 1 and 3 indicate that the theoretical
COD of all chemicals sewered for black-and-white processing at this install
ation is 217,000 Ibs 0') per year. The average COD of the effluent is about L
1750 ppm *. Acceptable pollution control would require sufficient oxidation
* Also, see Table 5
- 38 -
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of the effluent so that the -BOD5
would be about 300 ppm. This would call
for an effluent·with a COD not. greater than 500 ppm; or, the removal of
70 to 75% of the total COD. Annually, about 150,000 Ibs of COD should be
removed by chlorination.
1. Adequate chlorination of the effluent to
guarantee operational security will require a thorough oxidation of the
effluent, including destruction of organics. If organics are destroyed,
about 200,00.0 Ibs of COD must be removed by alkaline chlorination. The
weight ratio of caustic to chlorine required in. this case would be high;
probably, about two to one.
i. The quantity cost for chlorine varies from about
$0.04 to 0.23 per Ib, depending upon source and container size (see
Table 7). Sodium hydroxide is commercially available at $0.07 per Ib as
a 50% (by wt) caustic solution.
2,0 If' chlorine is purchased in I-ton cylinders,
the chlorine cost wil;L be $0.27 per Ib of COD removed. The caustic
requirement is estimated at 1. 5' Ibs of sodium hydroxide for each 11) of
chlorine; cost is $0.47 per Ib of COD. The estimated chemical cost for
aJ,.kaline chlorination therefore is about $0.74 per Ib of COD removed.
The adequate treatment of the department 'effluent thus will cost al)out
$150,000 per year for caustic and chlorine.
6. The cost of treating selected effluents would
be proportioned to their COD content. Developers and fixers carry about
100 gil of COD. Therefore, the' cos·t of completely reducing the oxygen
demand of these processing effluents is about $0.15 per liter. For arrest
baths, containing about 40 gil COD, the alkaline chlorination cost is
$0.06 per liter, and for a dye-removal bath (12 gil COD), about $0 .. 02
per liter. If the above used processing solutions are combined, the
estimated cost would be about $0.1:2 per J,.i ter.
I. Assuming that some ppst-treatment is required
to re-adjust pH, to remove dissolved solids, and to dispose of solids,
the annual cost for chlorination could be as high as $200,000.
,.. 39 -
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Table 7
Chlorine Sources and Chlor:ination Costs
Chlorine Source
Gas:
Tank Car
I-Ton Cylinder
150-lb Cylinder
Sodium Hypochlorite (15% solution)
Calcium Hypochlorite (70% available C1
2)
(per Chlorine Cost
Ib C]:21 (per Ib of GOD)
0.04 0.18
0.06 0.27
0.13 0.58
0.20' 0.89
0.23 1.02
Chlorination Cost* (per Ib of COD)
0.65
0.74
1.05
1.35
1.48
* Includes the cost of sodium hydroxide required (rati0 of NaOH to chlorine is 1. 5 by wt); based on NaOH costing $0.07 per lb. as a 50% by wt .caustic solution.
-- 40 -
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8. Treatment of the chlorinated effluent with lilrie
and sulfuric acid to lower pH and to remove some dissolved solids would cost
an additional $25,000.
2. Labor, estimated at one man full time, would cost
an additional $25,000.
as follows:
10. Facilities required for a chlorination .system are
a. Two chlorinators, including controls, safety switches, alarms, etc.
b. Chlorine storage, hoist, etc.
c. Two storage tanks, 3000 gal. size
d. Lime treatment and solids removal equipment
(d) Conclusions:
TOTAL
$12,000
3,000
5,000
5,000
$25,000
1. Hypochlorination will not adequately treat
processing wastes of this department.
2. Alkaline chlorination will satisfactorily reduce
the COD/BOD and destroy the processing flags of photographic wastes ..
1. The chlorinated effluent shoula be post-treated
to adjust acidity and to remove sulfates.
4. Capital costs for chlorination are· relatively
inexpensive; about $25,000.
.L. Chemical cost for chlorine ana caustic to
adequately treat department waste would be about $200,000 per year; about
$0.45 per gallon of (concentrated) processing solution.
6. These chemical .costs probably are too high to
consider this method of treatment.
- 41 -
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f. Evaporation:
(1) General:
TOP SI!CRETI I BI F-OOB-B-oo624-I-70-
(a) The evaporation or concentration of fluid wastes is 16-18 commonly used as an abatement step in the treatment of numerous wastes •
In photographic processing, the developers, fixers, and stop baths account
for most of the pollution while pollution from the dye-removal bath and
rinse water is small. By changing the plumbing of the machine, all of the
processing effluents could be combined and separated from the rinse water.
Thus, only 3 to 5% of the total department effluent need be treated by
evaporation; i. e., about 470,000 gallons per year (see Table 2).
(b) fi3everal types of equipment are commercially available
for the concentration of aqueous solutions:· single and multi-effect evapo
ration will provide concentration of wastes batch-wise; thin-film e,vaporators
operate continuously to concentrate a fluid; and spray-dryers provide another
means of removing solids from an effluent. Labor requirements for ·batch
evaporators are generally higher than for continuous, thin-film evaporators.
Initial costs for continuous equipment are, however, higher.
(c) A disposal area for solids and trucking faci.H ties
to handle about 350 tons per year (7 tons per week) would be required.
(2) Experimental. A known volume of the processing solution
waS 'placed ina measuring beaker and allowed to evapGrate gently at its
boiling point on a hotplate. As the sample volume was reduced, it 1;.ras
periodically cooled to room ambient temperature and seeded to initiate
crystal formation.
(3) Results:
(a) Sodium Fixer::
1. Two liters of a (fresh) sodium fixer were placed
in a stainless steel dish and heated to the boiling point (216F) on a hot
plate. After a 60% reduction in volume, the contents were allowed to cool
to room ambient temperature (80F). No solid phase formed.
16-18 See References.
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~. Evaporatton was continued giving an 80% reduction
in volume; then upon'cooling, a white solid cake of dry crystals formed,
which weighed 590 to 600 grams.
3. Sulphur dioxide was not detected (by odor).
(b) Combined Processing Solution:
1. One liter of a concentrated combined processing
solution (see paragraph 4.e.(4)(a) on page 31) was reduced in volume to
200 cc and allowed to cool. Some solids formed, but a liquid phase also
remained.
2. After reduction to only 100 cc, the residue
consisted primarily of light tan, granular solids; some liquid still
remained.
}. Upon reo_ucing the sample to 65 cc, no liquid
remained. The moist, light tan residue consisted of granular material as
well as strands of fibrous SDlids.
evaporation.
(4)
$0.05 per gallon.
4. Sulfur dioxiCLe was not detected during the
Costs:
(a) Energy costs for evapDration would be about $0.04 to
If all of the processing effluents (excluding rlnse
water) were treated, the cost for steam 0r gas heat would be $20,000 to
$25,000 per year.
(b) In addition to the heat costs, additional expense
for packaging, trucking, and disposal of the solids is estimated at
$25,000 per year.
(c) Capital costs for large volume equipment (installed)
will be about $1.00 p~r gallon per day. However, thin-film evaporators or
small evaporative units are much more expensive: e.g., c0ntinuous C1)ncen
trating system for 300 to 5000 gallons per CLay would cost about $50 ,000
to $75,000 (estimated).
- 43 -
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(5) Conclusion. Assuming a disposal site for solids is
available, the concentration of this department's processing effluent
by evaporatiGn or spray drying should be considered.
g. Pyrodecomposition:
(1) General.
(a) The Zempro Process (the high temperature wet oxidation
of fluid wastes) is a patented system for the smokeless incineration19- 21 of
biological wastes. The method has commonly been u~;,ed for the disposal of
the sludges from primary and secondary sewage treatment. The heat pro
duced in large uni.ts is generally adequate fGrgenerating the electricity
required for operation of the sewage plant. The ash produced is almost
completely inorganic, innocuous, and biologically sterile.
(b) Recently, fluid waste b1.1rners have been designed
to vaporize and oxidize both aqueous and non-aqueous chemical wastes. If
the heat of e0mbusion of the solvent plus solute is above 75,000 BTU/gallon,
generally no supporting fuel is required. With aqueous wastes having
little or no calorific heat value, vaporization, thermal decomposition,
and oxidation are achieved by either an oil or gas-fired burner.
(c) Several manufacturers claim efficient and economical
application of wet incineration to aqueous wastes. Several eommercial
units are equipped with scrubber equipment to remove gas or particulate
air contaminants. The stack gases are generally colorless and odorless
due.to the high combustion temperatures (1000 to 2200F) and long dwell
times.
(2) Experimental. Two synthetic processing wastes were
prepared from the proper proportions of developer, fixer, arrest, and
dye-removal solutions. (See Table 5). Samples of these effluents w"ere
sent to an outside laboratory for combusti0n tests.
(3) Results.
(a) The waste was found to have a very meager heat
value; i.e., 150 BTU/lb.
19-21 See References.
- 44 -
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(b) After ignition, the residue measured 6.75% by wt
of a highly-basic, water-soluble ash.
(4) Costs.
(a) Since there is very little ,fuel value to th!? solutes,
the energy costs will be about the same as for evafl0ration; 7,500 BTU per
Ib, qr $0.04 to 0.05 }'ler gallon.
$100,000.
(b) Costs for g~s and labor will be $55,000 per year.
(c) Equipment sized to handle 125 .gph will cost about
(5) Conclusions.
(a) Pyrodecompo~;ition of the more concentrated pro
cessing effluents (i.e., developers and fixers) should be considered.
(b) Arrest and dye-removal baths could also be treated
by pyrodecomposition; but, there are more economical, adequate methods.
h. Ozonation:
(1) Description.
(a) An alternate chemical method of lowering the
BOD/COD, destroying toxic materials, and removing processing flags is
by ozonation. As in chlorination, sulfites and thiosulfates are oxidized
to sulfates, and other organics are oxidized to carbon dioxide and water.
Ozonation, however, does not add to the dissolved solids total as does
chlorination.
(b) Ozonation has been used in tertiary'treatment
plants on effluents cont~ining organics 22 • The destruction of cyanides
and ferri/ferro cyanides is reported to be more efficient by oz(mation ,
than by chlorination.
(c) Theoretically, 1. 5 Ibs of ozone are required for
each pound of COD or BOD removed.
(2) Costs.
(a) The electrical pGwer costs for the production of
ozone by an electrical generator is reported to be $0.15 per Ib of 03.
22 See References.
-,' 45
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Approved for Release: 2018/06/25 C05039582
TOP S!CIU!T I ~---~ B I F-008- B-ooiil24-I-70- (b)( 1 )
(b)(3)
The energy cost of reducing the COD by ozonation is therefore about $0.22
per Ib of oxygen demand, or about· one-third that of chlorination. Annually,
the power costs for producing the ozone required would cost $45,000; or,
about $0.10 per gallon of effluent treated.
(b) To produce the 300',000 Ibs /yr of ozone required by
the treatment center for this department, capital costs would be about
$500,000.
(3) Conclusions:
(a) Reduction of the COD/BOD and destruction of organics
by ozonation would be cheaper than by alkaline chlorination.
(b) Ozonation would not ~dd dissolved solids to the
effluent.
(c) The major disadvantage to ozonation is the initial
cost of the ozone producing equipment.
i. Reverse Osmosis, Dialysis/Electrodialysis, and Ion E:xchange
(1) General:
(a) Applications for these physical methods are generally
limited to the pl.:l.rification of "brackish" waters or feed solutions having a
low solids content; i.e., 0.1 to 5%. Their main value is in water conserva
tion and not as final-treatment methods for pollution control.
(b) Of these four physical methods, reverse o;:;mosis (RO)
has been most thoroughly investigated and tested for water conservation
with photographic processing solutions 23,.
(c) RO units employing cellulose acetate membranes have
been used to treat wash waters from the Versamat and other proces:30rs ~
Some specific findings from these studies are as follows:
1. The pH of the product water changes very little
with treatment.
2. The average retention ratios of most ions found
in processing effluents are high:
a. Thiosulfates (e.g., Na2S203)'- 97 to 1
b. Sulfites (e.g., Na2S03
) - 63 to l
c. Acetate (e.g., acetic acid) - 98/99 to 1
d. Ferri/ferro cyanides [:.g., Na4Fe(CN)6] - 98 to 1
23 See References.
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TOP SECRETI ~---~
• Approved for Release: 2018/06/25 C05039582
Handl e 'Ii a BY EM AN Control System Onl y
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TOP S~CRETi"--1 _~----" B I F-008- B-00624-1-70- (b)( 1 ) (b)(3)
e. Bromides (e.g., NaBr) - 100 to 1
f. Dichromates (e.g., K2
Cr2
07
) - 94 to 1
~. Hydroquinone - 88 to 1
3. Some compounds, however, have a very low
retenti on ratio:
Ei. Benzyl al'cohol - 8 to 1
b. Formalin - 4 to 1
c. Elan - 2 to 1
4. At an operating pressure of about 600 psi, RO
units tested with the Versamat (Model lIA) Processor satisfactorily puri
fied wash water for re-use; these units cut consumption of water by 25%
without affecting the residual hypo level in the film processed.
5. For very dilute feeds, as with some rinse waters,
98% recovery of the water has been achieved. For more concentrated feeds,
the purified product may contain 10% of the initial impurity levels and
recover 90% of the water.
6. Flux rates obtainable will vary with fe'ed type
plus concentration, output rate aDd purity, pressure,' and membranes; but
a range is 0.05 to 0.30 gal/day/sq ft of membrane.
7. Commercially available units are offered by
several companies; the units vary in size from small laboratory experimental
models (2 gpm) to large industrial units (1 mgd).
(2) Costs:
(a) Operating costs (for utilities) are about $0.60
per 1000 gallons of reclaimed product.
(b) Capital costs for: typical large units are about
$1.00 per gallon per day. Thus, a unit to treat wash-water effluents of
this department would cost about ~S35 ,000.
(c) Small laboratory or experimental units can be
purchased for about $2000 and will deliver 2 or 5 gallons per minute.
(3) Conclusions:
(a) Reverse osmosis could be used to treat wash water;
this method will reduce wash-water consu~ption by 75%.
- 47 -
TOP SECRETI ~ ___ ----l
. Approved for Release: 2018/06/25 C05039582
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(b) Dye-removal and arrest baths could be treated by
reverse osmosis. Reverse osmosis 1ITould give a more concentrated (lOX)
effluent for disposal by other pollution methods and would give a purified
product that could be reused for wash water.
(c) The concentr(;l,ted effluent from a RO unit would
require treatment by other pollution methods, such as incineration, evapo
ration, chlorination, etc.
5. Separate versus Combined Treatment:
a. As indicated by Paragraph 3.c. (3)(d) on page 17, the 'Nash
water effluents require no treatment and may be sewered directly. All
other processing effluents will require some treatment, either to reduce
pollution or to maintain operational security.
b. The separate treatment of arrest and dye-removal baths by
reverse osmosis (RO) is the cheapest method studied. The concentrated
stream could then be treated by evaporation or pyrodecomposition and the
purified produc·t water reused. (If water conservation were a prime
objective, the RO equipment should be sized to treat the wash water,
jointly. )
c. Developers and fixer baths are adequately treated by bio
chemical oxidation, alkaline chlorination, evaporation/concentration,
pyrodecomposi tion, or ozonation. Thes'e effluents could be treated
separately or in combination by these abatement methods., A study of
the costs (see Table 8), however, indicates that there are no savings
in operating costs by considering separate treatment of developer or
fixer by these methods. Developers and fixers should be combined.
d. If RO equipment is used for concentrating the dye-removal
and arrest baths or wash water, these concentrates also should be com
bined with the used developer and fixer solutions.
6. Acceptable Treatment Methods:
a. Biochemical Oxidation:
(1) A biological treatment tank sized to handle about 500 lbs
of BOD in 40 to 60,000 gallons /da;.'f would be the cheapest treat)Uent studied.
An activated-sludge system would require an estimated tank volume of
12,000 cu ft. The effluent then could be sewered without further treatment.
- 48 -
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Approved for Release: 2018/06/25 C05039582
Handle via BYEMAN Con tro I System On I y
(b)( 1 ) (b)(3)
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Table 8
Estimated Costs of ~ollution Abatement Proposals
Capacity Required
Annual volume (liters)
Daily' average (liters/day)
Treatment ~etpods
Acidification/aeration:
Initial Cost (Equip. + Install.)
Operating Cost (Labor, Chemicals, Power, etc.) per 1000 liters
Biochemical oxidation ~ . (Note 2)
(b)( 1 ) (b)(3)
Initial cost (equip. + Install.)
Operating Cost (Labor, Chemicals, Power, etc.) per 1000 liters.
Annual Operating Cost**
Alkaline Chlorination (Note 2)
Initial cost (equip. + install.)
Operating Cost (Labor, Chemicals, Power, etc.) per 1000 lite~s
Annual Oper~ting Cost
Concentrated Processing Effluent* Developers
1,745,000
5,800
Partial
$ 5.00
75K
$15.00
25K
15K
$ 120
200K
1,212,000
4,000
Partial
$ 2.00
$150
159,000
Arrest Fixers Baths
283,000
950
187,000
625
Partial Note 4
$ 13.00
$160
40,000
$ 60
10,000
Dye Removal
Baths
62,500
210
Complete
10K
$ 4.00
$ 20
1,000
Wash Water
lLf, 000,000
60,000
Note 3
Note 1
Note 1
(b)( 1 ) (b)(3)
* This effluent contains all of the used processing solutions (i.e., developer, fixer, arrest bath, and dyeremoval bath); ~ash (rinse) water is excluded from this effluent.
** Determined by multiplying Annual Volume (liters) by Operating Cost per 1000 liters.
Approved for Release: 2018/06/25 C05039582
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Table 8 (cont'd)
Estimated Costs of Pollution Abatement Proposals
Treatment Methods (continued)
Eva]Joration/concentration
Initial cost (equip. + install.)
Operating cost (labor, Chemicals, Power, etc.) per 1000 liters
Annual Operating Cost
Pyro~ecomposition
Initial Cost (equip. + Install.)
Operating Cost (Labor, Chemicals, Power, etc.) per 1000 liters
AmlUal Operating Cost
Ozonation
Initial Cost (equip. + install.)
Operating Cost (Labor, Chemicals, Power, etc.) per 1000 liters
Annual Operating Cost
Reverse Osmosis
Initial Cost (equip. + Install.)
Operating Cost (Labor,Cbemicals, Power, etc.) per 1000 liters
NOTES: (1) Included in treatment of concentrated processing solution. (2) Applies to all effluents, including wash water. (3) No treatment required. (4) Method does not apply.
Approved for Release: 2018/06/25 C05039582
Arrest Baths
$20.00
$20.00
$ 20
$0.20
.Dye Removal
Baths
$20.00
$20.00
$ 10
$~O. 20
Wash Water
Note 3
Note 3
Note 3
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(2) The annual operating cost is estimated at $25,000 per year
.(or $15.00 per 1000 liters). The initial cost of the facility, about
:~lOO ,000.
b. Evaporation/Concentration:
(1) This second choice of treatment is predicated upon the
location of a sui table means of solids disposal, either by land-fill or
by incineration. Maintaining operational security would reQuire special
procedures in the disposal of the solids.
(2) The energy costs of concentrating photographic processing
solutions are comparable to those for biochemical treatment. Solids
disposal will double the operating expense estimated at $55,000 per year.
c. Pyrodecomposition~
(1) The incineration of the concentrated fluid w'aste has
the advantage of destroying all of the processing chemicals. The remain
ing solids (mostly sodium sulfate) therefore are innocuous and may be
sewered without jeopardizing security. Solids or residue disposal are not
a problem, since their removal is l)y the stack-gas scrubber:, this effluent
may be sewered.
(2) The eQuipment and full costs for pyrodecomposition are
higher than for evaporation.
d. Ozonation:
(1) Treatment of all processing effluents, im:luding rinse
water, with ozone is also an acceptable method.
(2) The electrical costs for ozonation are cheaper than the
chemical costs for alkaline chlorination. However, eQuipment for producing
the ozone reQuired for this installation is expensive; ab0ut $500,000.
e. Reverse Osmosis (RO):
(1) RO eQuipment would adeQuately treat arrest and dye
removal baths. If evaporation, pyrodecomposi tion, or trucking of the con
centrated developer and fixer are adopted, the arrest and dye-removal
effluents should be pretreated by RO. The concentrated product can then
be treated along with the developer and fixer.
(2) Initial cost for RO eQuipment to treat arrest and dye
removal baths would be $35,000. The annual operating cost for labor,
chemicals, power, etc. will be about $7,500 per year.
- 51 -
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Approved for Release: 2018/06/25 C05039582
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PILOT TESTING STUDY
1. Introduction
a. Treatment studies indicated that either one of two approaches
should be made towards acceptable pollution control· for· the department:·
(1) All effluents from the department, including rinse
water, should either be treated by alkaline chlorination or by a biolo
gical oxidation system; i. e., activated-sludge Gr trickling filter; or
(2) The used processing solutions should be combined (rinse
water excluded), and this concentratea waste treated either by incineration
or by evaporation/concentration.
b. To determine performance aata on actual processing waste
samples, two synthetic waste concentrates were prepared from used pro
cessing solutions. Both effluents are representative of wastes anti
cipated in 1970 ana 1971. They are similar in composition, except that
Type A effluent contains used, desilvered, sodium fixer solution; whereas
the desilvered ammonium (KRF-type) fixer was used in Type B effluent
(See Table 5). 8. Evaporation/Concentration
a. General: A dozen or more manufacturers of evapor.ation
equipment were contacted and given general information on the volume and
properties of the waste to be concentrated. The problem was described
to each equipment manufacturer as follows: Evaporate 2000 to 3000 gallons/
day of an aqueous waste containing about 1 Ib/gallon of aissolved s01ids.
Depending upon the response received., follow-up included requests for rough
sketches and. price estimates, pilot-tests, or interviews with techn:lcal
representatives.
b. Preliminary Investigation. Numerous types of equipment were
proposed by the following companies which responded to inquiries from
this department:
(1) Acme Process Equipment Co. Acme proposed a rotary
concentrator having approximately 1400 ft2 of surface area. Their c:on
centrator·units measure 110 ft2
/modu1e, necessitating some 13 units at
a cost of $150,000. Drives and other equipment were estimated at an
- 52 -
TOP SECRETI ~---~
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additional $25,000 for an estimated equipment cost in excess of $1"(5,000.
Ne further action was taken after examination of their initial quotatien.
(2) Zoremba Company. Representatives of the Zoremba Co.,
which designs and makes many different tYFes of evaporator/concentration
equipment, indicated their unit would require 75-100 ft2 of evaporation
surface area. The unit would be 4 ft x 4 ft x 4 ft high and, with all
accessery equipment, would cost about $28,000. Delivery would be in
4 to 5 months from final design and. placement of order.
(3) Thermal Research and Engineering Corp. A submerged
combustion unit to concentrate the effluent was Froposed. by Thermal
Research and Engineering Corp. Estimated size of the evaporator unit
would be 3-1/2 ft in diameter x 4 ft high, not including a 1. 25 million
BTU/hI' burner unit (fuel oil or gaB-fired) and a blower to supply 12:50
cu ft/hr of hot air. The estimated cost quoted was $10,000. The sub
merged combust.ion unit would also require solids removal equipment, such
as a rotary vacuum filter. Heat recovery from the unit was not deemed
feasible.
(4) Artisan Industries. An Artisan "Rothotherm" evaporator
was demonstrated. This unit is best described as a non-mechanical thin
film evaporator. Estimated size to handle 125 gallons/hour was 4 ft x
6 ft x 27 ft high with equipment costs of $10.,000 to $12,000 without
accessory instrumentation.
(5) Stern-Rogers. As a result of their studies on an
effluent sample supplied them, Stern-Rogers proposed a Rotary Dehydrator
(Drawing #13209/2). The direct-fired concurrent-flow unit would be about
3 ft in diameter x 12 ft long, including the refractory-lined air heater,
burner, and connections. Including a fan, damper, dust collector, and
all controls, the system was estimated to cost $24,800.
(6) Swenson. The Swenson Division of Whiting Corp. proposed
a standard single-effect long tube vertical evaForator unit. Estimated
cost for the evaporator, condenser, mounts, and controls would be $18,000 •
. - 53 -
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Approved for Release: 2018/06/25 C05039582
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A rotary vacuum filter syqtem for solids removal would be reCluired at an
additional unspecified cost.
(7) Batch Evaporators.. Single-effect evaporator uni t:3 can
be purchased Gr fabricated to evaporate 750 gallons per 8-hour trick.
Estimated costs of ope'ration are $150/day for 1500 gallons/day, bas'2d on
two-trick operation. This includes clean out, re-filling, and nece3sary
maintenance.
c. Pilot-Tests
(1) Pfaudler (Div. of Sybron) Thin-Film Evaporation
(a) Testing., A feasibility study using a 2-inch Wiped
Film Eyaporator Unit (WFE) indicated that waste from this department could
be concentrated and .so to 90% of the water removed by single or multiple
passes through their pilot unit. Consequently, arrangements were made
for shipping 100 gallons of Type A Effluent (See Table 5) to Pfaudler's
and for copducting a pilot-test on their 12-incll WFE unit.
(b) Results. Table 9 summarizes the results of these
pilot runs. The COD measurements on the distillate fractions were deter
mined by a standard analytical method 24 The pilot test indicated that
the Pfaudler unit was not capable of more than a 65% distillate-to-residue
spli t,~ , The apparent reason for this low efficiency was due to the (~logging
of the unit by the 'formation 'of a ,gelatinous residue, which attached itself
to the ~iper blaQes. Further examination of the unit revealed that the
many entrainment separators, wiper blade flanges, and other component
ledges offered numerous points for the solidified residue to become
trapped. The best performance in terms of distillate properties was
obtained wllen the unit was operating under a vacuum. At a reduced pressure
of 120 nun (abs), the COD of the distillate was well under 1000 ppm, as
compared with 2000 to 3000 ppm for operation at atmospheric pressure.
(c) Conclusions: The Pfaudler thin-film evaporator will
not adequately concentrate effluent of this department without major rede
sign to avoid clogging problems 25.
(2 )Votator "Turba-Film" Evaporator:"
(b)( 1 ) (b)(3)
"( a) Testing. During two days of testing, thirteen pilot
runs were made using a 1 sq-ft thin-film evaporator unit at the Lousville, Ky,
plant of the Votator Division, Chemetron Corp. Two types of rotor blades
were used: a fixed-clearance (0.030 inch) and a hinged "Hydra-Film" rotor
wi th "Duron" blades, which actually wiped the inner wall. The operating
parameters were as follows:
l. Steam pressure - Atm. to 100 psig
2. Wall temperature - 212 to 350F
3. Feed rates - 55 to 70 Ib/hr
4. Rotor speed - 300 to 2100 rpm
5. Pressure - Atm. to 25 in. of Hg (vacuum)
(b) Results:
1. During the first runs with the fixed--clearance
rotor, there was a build-up of dried solids on the inner wall of the evap
orator. 'rhe residue fraction was comprised of polymerized hunks of white
solids, suspended in considerable amounts of water. The maximwn distillate
to-residue split obtained was 66 to 34%. The pH of the distillate was
gl to 10.5.
2. Tests with the "Hydra-Film" rotor were conducted
under similar operating conditions. Build-up on the inner wall did not
occur and the solids were discharged as a white, creamy fluid. As the
solids separation improved, the viscosity of this paste increased, but no
granulari ty was noted. Upon drying the residue (at 103C) , the solids
content was 71.5% by wt.
3. A distillate-to-residue split of 92 to 8% was
achieved on one test and, over a continuous 2-hour run, a 88 to 12% snlit
was achieved. The distillate fractions were clear and had a COD of less
than 100 ppm.
(c) Conclusions:
1. Pilot-tests showed that the I'Hydra-Film" evap
orator was acceptable in separating dissolved solids from effluent of this
25 See References.
- 56 -
TOI' SECRET) '--___ -....J
Approved for Release: 2018/06/25 C05039582
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department. The separation gave a viscous, creamy-looking residue with
Ii ttle free liQuid and sui table for solids disposal in a reduced volume.
The distillate would be sui table for dumping into the sewer and a 10 t.o
1 reduction in volume could be achieved by this evaporator eQuipment.
2. This method would require disposing five
55-gallon drums of a highly viscous slurry each day.
(3) Conical Bottom Laboratory Spray Dryer.
(a) Testing. Feasibility tests on the spray-dyying
of effluent from this department were conducte'd on Bowen t s Conical Bottom
Laboratory Spray Dryer. This gas-fired unit was operated over the
range of conditions listed below:
l. Feed rate 230 to 360 mIs/min
2. Feed temp 65 to l25'F
3. Gas inlet tem:rv 400 to 700F
4. Gas outlet temp 230 to 4l5F
Two types of atomization were tested: a two-fluid orifice (air plus the
feed) and a centrifugal atomizer. By the proper adjustment of the abcwe
parameters, a thoroughly dry, powdery residue was obtained from the
effluent. The stack gases were nearly colorless, odorless, and a;:; much
as 75% of the solids were recovered in the cyclone dust collector.
Table 10 summarizes the feed conditions, operating conditions, and material
balance of the Bowen pilot test.
(b) Pilot-Test. Eight pilot runs then were made with
Types A and B effluent * in a 7-foot diameter spray-dryer. The o:perating
parameters were similar to those of the feasibility test, except that
atomization was accomplished by a high-speed centrifugal atomizer. During
the runs, the stack gases were checked and sampled for odor and particulates.
(c) Results
1. For either type of feed (Type A or B), the
drying chamber could be operated almost clean when the air inlet tem
perature was 500 to 600F and the air outlet temperature was 320F.
Slightly better atomization was achieved when the feea was heated to
* These effluents are similar in composition except that Type A contains used, desilvered sodium fixer solution, and the Type B contains desilvered ammonium (KFR-type) fixer.
- 57 -
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Handl!! via BYEMAN (b)(1) Con t ro I System On I y (b )(3)
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RUN NO. DATE:
FEED CONDITIONS:
Identification Feed Make-Up
Type wt. % Solids Spec. Gravi.ty Temperature F
Feed Rate, lbs/min Total Feed, lbs
OPERATING CONDITIONS:
Inlet Temp. F Outlet Temp. F Type Heat Atomizer Type Atomizer Description Atomizing Force, Speed RPM Cold Air Utilization Chamber Conditions
MATERIAL BALANCE:
Cyclone Collector (lbs) Chamber Wall, (lbs) Total Collected (lbs) Total Solids Fed (lbs) % Recovery, Wet Basis
ANALYSIS OF CONDENSATES FROM STACK EFFLUENT
pH Color
COD (ppm)
S03= as Na2S03
(gil)
+ N ,as NH4 (gil)
1
Table 10
Bowen Pilot Test
2 3 4 APRIL 7 , 1969
5
- - - Effluent Residue Solution - - -- Type 'A' - As Received - -
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(2.) Sampling and Analysis
(a) A lacal independent testing agency was contracted
to' manitar same af the aperating parameters, callect stack gas samples,
amI analyze far particulate ar chemical pallutants during the pilot runs
an the waste. The results are shawn in Table 12. The unit was operated
an bath types af effluent at 20 gal/hr.
(b) The emerging stack gases were faund to' range in
temperature fram 1000F to' as high as 2100F. Stack gas valumes at these
temperatures ranged fram 4050 to' 3300 efm.
(c) The carban diaxide cantent af the stack emission
was 2.8% (by valume) far bath feeds. Ammania cantent was negligi'ble.
The carban manaxide, axygen, axides af nitragen, and axides af sulfur
were significantly different far each feed type. The highest carbon
manoxide cantent (2.6%) and sulfuT diaxide (2.46 ppm) came fram the
Type A (sadium fixer) feed. The highest cancentratian af nitragen axides
(167 ppm as l'J02
) in the stack gases was observed with the Type B (ammanium
fixer) Feed.
(d) The smake ar plume density was well under 20%
ar less than Ringelmann Chart #1. The particulate matter callected
was campletely water saluble and slightly acidic. The mean particle
size was 10 micrans, with an abserved range af from 1 to' aver 150 micrans.
Attempts to' callect an adequate sample of particulate matter for further
evaluation were not successful.
(3) Canclusian. Thes tests demanstrated that pyradecampa
sitian ar incineratian would render suitable treatment far a combined
aqueaus phatographic waste. Further testing wauld be required to' determine
whether ar n0t the stack gases contain excess settleable particulate
matter and to' select suitable equipment that cauld be used with an adequate
stack gas scrubber.
(L~) Equipment Size and Cast. A unit sized to' handle about
75 gal/hr (average) wauld require a concrete pad abaut 10xlO'ft and wauld
be approximately 28-ft high. The equipment cost w0uld be about $40,000,
including remate contral panels and safety interlocks.
- 62 -
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TO .. SECRETI BI F_008_B-00624-1-70- (b)(1) (b)(3)
Test Unit:
Test Condi tie:)Ds:
Table 12
Incineration Pilot Test Results 26
Prencots Super E..., Pyrodecomposition Unit :) ,
Date: 25-26 September 1969 Feeds: Type A Effluent
Type B Effluent Feed Temperature: 70 ± 5F Feed Rate: 20 gallons per hour Fuel: Natural gas
Sampltng and Analyttcal Procedures:
Reference: Holmes Source Testing Manual, Atr Pollution Control Dtstrict, Los Angeles Co., Caltfornia (1963)
Results:
A.
B.
C.
stack gas measurements
Gas volume: Gas temperature: Motsture content:
3300 to 4050 cfm 1000 to 2100F 8.7 to 11.0% by volume
Stack Gas Analysis (by volume)
Type "A" Feed Type "B" Feed
Carbon dioxide Carhon Monoxide Oxygen Nitrogen
Oxtdes of BHrogen (as N02)
Oxides of sulfur (as SO~)
Ammonta
Parttculate (for botb feeds)
Stze:
2.8% 2.6%
12.2% 73·7%
80.6 ppm
24.6 "
Less tban 0.16 ppm
1. range: 2. mean:
Less tban 1.0 to over 150 mtcrons 10 mtcrons
Amount: Negligible
2.8% 0.6%
16.0% 79·6%
167. 6
'10·9
Less t,hs,n
Denstty: "Smoke" or plume denst ty less tban, 2:0% or Rtngelmann Cbart 1
Water Solubiltty: Very soluble and sUgbtly a:ctdic (pH = 6.4)
0.16
26 See References. - 63 -
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,b. John Zinc Co.
(1) Equipment
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(a) An incinerator system proposed by the John Zinc Co.
will.thermally decompose and oxidize aqueous effluent of this department
and adequately remove pollutants from the stack gases*. The system
woula cons ist of four components; namely, burner, a thermal oxid:izer,
a quencher, and a Venturi-type scrubber. The scrubber would. remov'e
. and sewer any gaseous and particulate contaminants from the stack gases.
(b) To treat 125 gal/hr of aqueous waste, the burner
would consume about 4 million BTU/hour. Either gas or oil can be used
to heat the thermal oxidati0n unit from 1400 to 1600F. The hot gases
then are cooied to about 200F ~n a direct-spray control chamber, 'before
entering the high-energy Venturi scrubber. The system would require a
20- x 40-ft area and a 50-ft stack. Total es-timated weight is 50,000 lb.
(2) Cost. The quoted price, including all controls, start
up engineering service, etc., is $75,000.
c. Other Incinerators:
(1) Units s.imilar to the Preneo aesign were proposed by
Peabody Engineering Corp (Stamford, Conn.) and the Hyaro Combustion Corp.
(Santa Fe Spring's, California).
(2) The Peabody Liquid Waste Combustor properly sized to
handle 125 gal/hr, would cost about $25,000. This system could also
be either gas or oil fired, and should include a Venturi-slot ga:s
scrubber. '
(3) The units designed by Hydro Combustion C0rp are supplied
in five standard sizes ranging from 20/hr to 500 gal/hr. The cost of a
unit to handle 20gal/hr is about $16,500 (for complete package).
*
10. Solids Waste Disposal
a. Several proposed methods of pollution a1:Jatement are predicated
Eastman Kodak Co. (Longview, Texas) is presently involved with the John Zinc Co. in the development of a suitable waste disposal system for treating/incinerating aqueous acetonitrile waste.
.,. 64 -
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upon an acceptable means of disposing solid waste; for example:
(1) A thin-film continuous evaporation unit would yield
about 4000 Ibs/day (maximum) of a thick slurry (75% by wt) of photographic
chemicals.
(2) The flash-evaporaticm (or spray-drying) of the concen
trated effluent would yield up to 3000 lbs/day of .dry, powdery chemical
waste.
(3) Chlorination, followed by a lime treatment to remCNE
dissolved solids, or a chemical precipit1;l.tion approach, would produc:e
ab8ut 2 to 3 tons of calcium. sulfate :per ".day.
b. The waste from methods (1) and "(2) would be mostly water
soluble; the produce from method (3) would be essentially water insoluble.
c. Disposal of a water-soluble waste by land-filJ generally
":presents problems since runoff from" t"he site may be polluted."
d. The disposal of a "\vater insoluble waste, such as one which
consists mainly of calcium sulfate, appears to be feasible. A formal
request was therefore made to management "to investigate the possibil.i ty
of trucking 2 to 3 tons per day 'of ,-Taste to an industrial disposal site.
11. Alkaline Chlorination
a. Test Objective. These pilot studies were c;onducted to
prove' the feasibilj.ty of reducing, tlle oxygen demand of a processing
effluent by alkaline chlorination and to determine the chemical costs
of chlorination.
b. Pilot Equipment
(1) The alkaline chlorination :pilot unit shown in Figu.re 1
consisted of a closed loop system with two 10 gallon polyethylene tanks;
a circulation pump; connecting lines, rotometers, and valves; and a small
chlorine-gas injector unit, capable of delivering 4 Ibs/hr of chlorine
gas from a 100 Ib supply cylinder. The system was assembled under a
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(c) The stack-gas quencher and scrubber unit, and
(d) The stack.
(5) Rinse water can be used in the quencher/scrubber unit
and then sewered. The temperature of this wastewater should be ma:tntained
below 100F. This wastewater will contain an increased amount of dissolved
solids, mostly sodium sulfate.
(6) An Incineration System
(a) Based upon Michigan Testing's sampling and analysis
while Prenco's Super E3 Pyro-decomposition unit was operating at 25 gal/hr
on effluent from this department, the stack emissions will meet all existing
applicable air pollution codes with the possible exception of particulate
matter. Theoretically, this department should have as much as 75 lbs/heur
of ash or residue from an incinerator operating at 100 gal/hr. H01treVer,
Section 8 of the Menroe Co. Air Pollution Code establishes a limit of 2.5
lbs/hr as rate of feed for this department. Thus, a scrubber may 'be necessary
to remove about 97% of the ash (theoretically) expected from this department's
waste. It should be noted that actual measurements of the s·tack emission
for p§.rticulates with Prenco's incinerator did not exceed. the particulate
limitation set by Section 8 of the existing code.
(b) If it is found necessary (after installation) to
collect and remove ash and/or fly ash from an incinerator unit via a
scrubber unit, two following approaches are pos.sitJle.
1. A dust collector (centrifugal, electrostatic,
.or bag house type) would remove an ,estimated 150 tons/year of solids,
consisting mostly of sodium sulfate (Na2
S04) and oxides of sodium, potass.ium,
aluminum, boron, etc. This by-product could not .be readily associated with
photographic processing and, therefore, its. disposal could be mad.e in most
any solids waste area.
2. A wet scrubber (spray, impingement, or baffle
type) can be used and the scrubbing selution sewered. In this case, the
residue from the scrubber would increase the total dissolved solids of
this department's sewage to about 3400 ppm (average annually) or about
0.50% bywt under the ~ conditions. This minor contribution to "water
pollution" would be acceptable under the City Sewer Code.
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14. Treatment of Toxic Effluents. Photographic effluents may be
considered to be non-toxic industrial wastes, provided color bleach,
dichromate cleaners, and fungicide solutions are excluded. Color bleach,
cleaning, and fungicide solutions are discussed below.
a. Ferri/Ferro Cyanide Bleach
(1) The preferred pollution abatement step for ferri/ferro
cyanide bleach is regeneration and re-use.
(2) When color bleach must be disposed of, alkaline chlori
nation will effectively destroy ferri/ferro cyanide and render color
bleach waste non-toxic and low in BOD.
(3) The chemical costs for complete treatment of a typical
(b)( 1 ) (b)(3)
color bleach (containing 250 gil of potassium iron cyanide) is $1.00 per liter.
(4) Alternate methods of bleach treatment (such as elec
trolysis, ozcmation, and incineration) should be explored and pilot
tested.
b. Cleaning Solutions
(1) Cleaning agents containing dichromates * should be
,avoided, since most city codes prohibit the discharge of wastew:ater con
taining chromium or "heavy metals".
(2) A suitable, non--toxic cleaning agent for the fix and
wash equipment is chlorinated trisodium pbosphate, used at a concentration
0f 1 oz/gal.
(3) A suitable non-toxic cleaner for develo.per equipment is
a mixture comprised of 75% (by wt) hypo plus 25% EDTA (mono-sodium ferri
salt), used at a concentration of '4 oz/gal.
c. Fungicide Solutions. The use of organic phosphorous r;om
pounds as fungici0.e solutions should be avoided. No anti-fungicide
treatment is required if chlorinated cleaning solutions are used.
15., Final-'J;reatment Proposal for Bli (Black-and-White)
a. All of the acceptable treatment methods investigated were
considered, but finally rejected for the BH facility. The specific
reasons for their rejection are as follows:
(1) Bio-oxidation system. Too. much area and volume re
quired for location at this facility.
* An example of a commercially available cleaner containing potassium dichromate, is Kodak :Developer Systems Cleaner.
- 19 -
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(2) Concentration by evaporation: This method requires
a solids disposal site, and no adequate land-fill is available. Further
more, the disposal of photographic residue from this department would be
a potential security pro1)lem.
(3) Incineration: ]~ocal air env'iromnental regulations re
quire that applications for the installation of all new incinerators be
approved, investigated, and tested by lO'cal health authorj.ties. 'l'hese
regulations present potential hazards to maintaining operational E:ecuri ty.
b. The alternative solution to an in-house treatment center was
therefore considered; name Zy, using an outside treatment faci li ty. The
costs for trucking to a near-by i,~dustY'iaZ uJaste treatment faciUty were
found to compare favorcibZy to the most economical in-house treatment
(biochemicaZ-oxidation).
16. Final-Treatment for LP (~:·olor)
a. Pollution abatement and control steps at LP
included:
(1) Reduction in fixer replenisher rates.
(2) Electrolytic desilvering, rejuvenation, and re-use
of fixer, and
(3) Regeneration and re-use of color bleach.
b. No final-treatment system was planned for this facility,
althcmgh the bio-oxidation method would be the preferred abatement.
- 80 -
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GuNCLUSIONS
17. Biochemical-Oxidation
a. The most economical, acceptable treatment method for photo
graphic effluents is biochemical oxidation.
b. All photographic effluents including rinse water may be
treated by this method jointly with the exception of color (ferri/ferro)
bleach, which should be excluded.
e. It will generally be advisable to use municipal treatment
facili ties whenever they are available.
d. An activated-sludge treatment tank is the most compact
system. The BOD load for photographic effluents is about 1. 5 to C~. 0
Ib of O2
per day per 1000 gallons of tank volume. The effectiveness of
the AS treatment in removing BOD is 90% or better.
e. By acclimation of the system, using oxygen instead of air
and by adding domestic sewage (or other nutrients), the BOD load of an
AS system can probably be raised to about 3.0 Ib/day/lOOO gallons.
f. The estimated treatment costs for a biochemical oxidation
system is $15.00 per 1000 liters of eoncentrated photographic effluent.
g. Equipment costs for the BH facility are estimated at $75,000.
The total annual operating expense (power, labor, and chemicals) vTould be
about $25,000.
h. A biochemical treatment facility for the BH facility sized
to adequately reduce the BOD would be prohibitive in size.
18. Incineration
a. Incineration of the concentrated, combined processing solu
tions is an acceptable alternative treatment method. The adoption of this
method necessitates equipment changes for the separation and eXClusion of
rinse water. Air environment codes may require corrective pollution abate
ment equipment for the stack emissions.
b. Rinse water from photographic processing generally constitutes
90 to 98% of the volume of the total effluent. It usually requires no
treatment and may be sewered without treatment.
c. The segregation and separate treatment by pyrodecomposition
of tfie concentrated prccessing solutions (i.e., used developer, fixer,
arrest, dye removal baths, etc.) reduces BOD/COD and pollutants by more
than 99%.
- 81 -
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d. The cost for incineration of used, processing effluents is
$32.00 per 1000 liters (about double that for AS treatment).
e. Equipment costs for the BH facility are estimated at $100,000.
Annual operating expenses (including labor, power, and fuel) would be
about $55,000.
f. The thermal decomposition and oxidation of the constituents
of photographic solutions give water vapor, carbon dioxide, carbon monoxide,
some oxiaes of sulfur and nitrogen, and a water-soluble arrest ash.
g. The use of a wet-scrubber may be required to remove particulate
matter; mostly, sodium oxides and sulfate. The effluent from the scrubber
has no BOD/COD, is non-toxic, ana may be sewerea.
h. The incineration of i;he effluent from the BH facility was
not recommended for security reasons: 'the nature and volume of processing
operations might be ascertained if local officials for the environment are
authorized to approve, inspect, and test aU new incinerator equipment.
19. Concentration by Evaporation and Reverse Osmosis
a. When maximum water re-use and conservation is a primary ob
jecti ve, the concentrated processing effluents (fixer,. aevelopers, etc.)
shoula be separated ana further concentrated by evaporation and the dilute
processing solutions (arrests, dye-removal baths, wash water) treated by
reverse osmosis. Land-fill and incineration are suitable methods for the
final disposal of the residue or concentrate.
b. -Evaporation of the concentrated processing effluents yields
a white solid or slurry and a condensate that can be re-1J-sed in photographic
processing. R~sidue-to-distillate splits in excess of one-to~ten have
been achieved by both batch and continuous evaporation equipment.
c. No suitable use for the residue has been established. The
suggested methods for aiposal are incineration or suitable land-fill.
d. Thin-film evaporators are suitable for concentrating photo
graphic effluents to a semi-solid slurry which can be easily handled.
e. The stop, -dye-removal bath and other processing effluents
having a low solias content may be combined and treated by reverse osmosis
(RO). The concentrate from the RO unit may be further concentrated by the
evaporator.
- 82 -
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f. Energy costs for evaporation are only $0.04 per gallon
($10.00 per 1000 liters), but the costs for labor and solids disposal
are expected to raise this value to about $32.00/1000 liter. Equipment
costs for a thin film evaporator unit which will handle 125 gallons per
hour will be approximately $75,000. Annually labor and power would
cost $55,000.
g. Power costs for RO are $0.60 per 1000 gallons of treated
wastewater.
20. Alkaline Chlorination for Color Bleach Wastes:
a. Color bleach wastes, containing toxic ferri/ferro cyanide
ions, require the following abatement steps:
(1) ,Reduction of carry-over volumes used by installation
of squeegee rollers.
(2) Regeneration and maximum re-use of all color bleach
solutions; and
(3) Adequate treatment of alkaline chlorination.·
b. Alkaline chlorination is the best established method of
destroying cyanide wastes.
c. The chemical costs are high; about $1.00 per liter for
a typical color bleach, or $2.00 per pound of potassium ferricyanide
treated.
methods.
d. This treatment is applicable by batch or continuous
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RECOMMENDATIONS FOR BH (Black-and-White)
. 21. Final Treatment
a. Separate the rinse vlater and Photo-Flo bath from all other
processing effluents; sewer without treatment.
b. Collect, desilver, rejuvenate, and re-use fixer solutions.
c. Combine used developers, stops, dye-removal baths, and any
used fixers; collect and store in storage facility (described in paragraph
12. c. )
d. Truck and treat in nearby biochemical-oxidation facility.
22. Facility Requirements:
a. Provide a waste line for collecting used developers,
arrests, and dye-removal baths from each processor.
NOTE: Photo-Flo and all other process water may be sewered using existing waste lines.
b. Install two 5,000 gallon tanks for effluent storage. If
uni ts are installed out-of-doors; each should be equipped with thermally
regulated heating elements (set for 26F minimum).
·c. Provide chemical dump lines from the collection tank
facility to the mix room, to the chemical laboratory, and to each processing
area.
23. Limitations, Restrictions and Future Efforts:
a. Establish a normal routine for trucking the effluent. from
the collection facility to the treatment facility to eliminate clues to
the cyclic nature of operations.
b. Restrict the use of chromic acid cleaners (e.g. KodE~
Developer System Cleaner).
c. Use bio-degradeable substitute cleaners whenever possible.
d. Periodically collect samples of effluent and analyse for
photographic flags, BOD, GOD, and other waste water characteristics.
24. Future Hardware Efforts:
a. Investigate commercially available biochemical-oxidation
treatment units. Conduct pilot-tests using black-and-white and color
processing effluents.
- 84 -
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b. Investigate small fluid waste incinerator units.
(1) Conduct pilot tests on processing wastes.
(2) Sample and analyze stack emissions for possible
air pollutants; and, if necessary
(3) Investigate and test stack-scrubbing equipment.
c. Test a thin-film evaporator and condenser system jOintly
with a Reverse Osmosis unit for water conservation.
25. Future Study Efforts:
a. Ozonation:
(1) Purchase a small (electric) ozone generator and test
the effectiveness of ozonaticln as a means of reducing the BOD/COD of
photographic effluents.
(2) Explore aerati~n of photographic effluents using
oxygen-ozone mixtures.
b. Bleach Treatment:
(1) Conduct la8oratory studies on the following approaches
to cyanide bleach treatment:
(a) Electrolysis
(b) Ozonation
(c) Alkaline cplorination, using catalysts.'
(2) Conduct pilot tests on the pyrodecomposition (:ncinera"':
tion) of bleach wastes.
(3) Pilot test alkaline chlorination of bleach, using
catalysts.
c. Computerized Pollution Program:
(1) Compile a card-file listing of the salt composition
and polluting properties of processing solutions.
(2) Establish a computer program for determining the
pollution magnitude of effluents from the various processing equipment
using the established processing chemistry and machine specifications.
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REFERENCES
1. FINAL REPORT, "Acceptable Pollution Standards", Contract EG_l±.Q.Q, Task 34. Section I, 16 June 1969.
2. FINAL REPORT, "Study of Pollution Contribution from Processing Activities", Contract EG-400 ft Task 34. Section VIII, 3'March 1969.
3. "Standard Methods for the Exa.mination of Water and Wastewater", American Public Health Assn. , Inc., N.Y., 12th Edition, 1965,.
4. Sewer Use Code, Code of the City of Rochester, Chapter 97, 1968.
5. Technical Memo, W. Wesley Eck.enfelder, Jr., "Economics of Wa~)tewater Treatment", Chemical Engineering, pp 109-118, 25 August 1969.
6. Chemical Engineering News, "Organics Tested in Waste Treatment", pp 42-43, 8 December 1969.
7. Chemical Week, "Equipment for a Dirty Job", 17 February 1968.
8. LawrenceK. Cecil, "Water Reuse and Disposal", Chemical Engineering, pp 92-104, 5 May 1969.
9. Mohanrao, G.J., et al, "Photo-Film Industry Wastes: Pollution Effects and Abatement", Central Publi.c Health Engineering Research Institute, Nagpur, India,' 1965. '
10. Eustance, H., "Treating Photo-Industry Process Waste", Indus-::,rial Water and Hastes, Vol. 5, 1969.
11. J.S. Sconce, Ed.-in-Chief, Am. Chem. Society, "Chlorine: It:, Manufacture" Properties and Uses", Reinhold Publishing Corp., N. Y ., 1962.
12. Data Sheet 207, National Safety Council, "Chlorine", Chicago, 1966.
13. Plating, "A Report on the Control of Cyanides in Plating Shop Effluents", pp 1107-1112, October 1969.
14. Weiner, Robert, "Effluent Treatment in the Metal Finishing Industry", Am. Electroplaters' Soc. Inc., N.Y., pplll-116.
15. U.S. Paterits #2,981,682 and l,i3.l0l,320issued to Leslie E. Lancy, Assignor to Lancy Laboratories.
16. Walter F. Swanton, "Inexpensive Answer to a Pollution Problem," Chemical Engineering, pp 128--130, 13 February 1967.
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REFERENCES (Cont'd.)
BI F-OOB- B-00624-1-7C(b)(1) (b)(3)
17. Donald F. Othmer, "Desalting of Seawater", Chemical Engineerj:E£., pp 205-209, 10 June 1963.
18. J.M. Culotta and W.F. Swanton, "Case Histories of Plating Waste Recovery Systems", Plating, pp 251-255, March 1970.
19. L. W. Coleman and L. F. Cheek, "Liquid Waste Incineration", Chemical Engineering Progress, Vol. 64., No.9, pp 83-87, September 1968.
20. Chemical Week, "Burning for Good Riddance", pp 59-60,8 May 1968.
21. E. S. Monroe, Jr., "Burning Waste Waters", Chemical Engineeri~, pp 215-221, 23 September 196a.
22. "02 and 03 - Rx for Pollution", Chemical Engineering, pp 46-48,
23 February 1970.
23. Chemical Week; "It's Full Speed Ahead for Reverse Osmosis", 3 August 1968.
24. "Standard Methods for the Examination of Water and Wastewater", American ·Public Health Association Inc., N.Y., 12th Ed., 1965.
25. Report, "Pfaudler Wiped Film Evaporator Test No. 277", 2 January 1969.
26. Michigan Testin~ Er.ce;ineerin~ Report No. PL-1Q.Q2, "Re]lort on the Quantity and Composition of Effluent from a Fluid Waste· Incinerator", by Carl L. Carlman.
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APPENDIX A
This appendix contains a reproduction of FINAL REPORT on
Section I, 16 June 1969. This report was published
28 July 1969.
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SUMMARY
SUBJECT
TASK (from Study Plan)
INTRODUCTION
1. - 3.
DISCUSSION
4. Pollution Magnitude
TABLE OF CONTENTS
a. Annual Chemical Usage b. Water Effluents c. Processing Solution Usage d. Sewer Samples
50 Established Pollution Standards
a. City Sewer Code b. Rules, Classifications, and Standards
for the State c. Federal Attitude and Standards d. Summary
6). Acceptable Security Control
a. Control Measures
Section I, Task 34
Page
4
5
5
5
5
6
6
6 9
10 13
18
18 20
20 21
b. Acceptable Department Waste Characteristics
21
21 21 22 22 24 25 25 26
c. Toxic Standards d. Non-toxic Standards e. Ammonium Compounds f. Photographic Flags g. Disproportioning Constituents h. Cyclic Variations
CONCLUSIONS
7. - 13.
RECOMMENDATIONS
14. - 16.
REFERENCES
APPENDIX i. - Industrial Waste Characteristics
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Table
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3 4
5 6
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11
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Section I, Ta.sk 34
LIST OF ILLUSTRATIONS
Title
Sampling Diagram of Plumbing Areas
Sampling Diagram of Plumbing Areas
LIST OF TABLES
Title
Color-
B&W
Chemical Usage and Pollution at BH (B&W)
Chemical Usage and Pollution at LP (Color)
Chemicals Causing Pollution at BH
Chemicals Causing Pollution at LP
1968 Processing Solution Use at BH
1968 Processing Solution Use at LP
Comparison of Pollution at BH vs. LP
1968 Summary of BH and LP Pollution Magnitudes
Industrial Waste Characteristics and Q,uantities
Non-Toxic Limitations for Wastes Accepted by City
Suggested Effluent Limitations
Aw~onium Ion Concentrations at Various pH Levels
Acceptable Department Waste Characteristics
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Section I, Ta,sk 34
SUMMARY
Safe levels of toxic and non-toxic pollutants are recommended for this
processing facility. When adhered to, the recommended standards satisfy
the requirements of both pollution abatement and security against disclosing
the nature of our operations.
Only the local city Sewer Use Code is directly applicable as a guide
for pollution standards. Even here, the local code does not cover the
majority of constituents characteristic to photographic processing facility
effluents. Because the code is subject to change or more strict enforcement
at any time, and also because of the contractor's concern for security and
the general nature of the pollution problem, standards are recommended to
cover a considerably wider scope of pollutants than given in the code at ,
present. In total, the standards encompass all conceivable sources of
pollution or of effluent clues to the nature of operations.
The results :indicate that either a single treatment or a series of
treatments is feasible to effect compliance with the recommended standards.
Further, the comprehensiveness of the standards will dictate the suitable
choices of treatment without requiring separate consideration of the two
aspects of the problem: pollution abatement and security.
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SUBJECT: Acceptabie Pollution Standards
TASK
A. Study-and define safe security standards as applicable to this project
for discarded chemicals via min:linum identifiable levels of processing chemicals
in this contractor's effluent.
B. Study and define a safe pollutant level or a scale of levels to which
each pollutant can be referred. This study would produce two major c:ategories:
. (1) Toxic standards, and (2) non-toxic standards. The standards that will be
adapted will conform with those for the building complex, that in turn will be
guided by local, state, and federal requirements.
INTRODUCTION
1. All photographic processing effluents from the contractor's 1'acili ties
at both LP and BH are discharged into the city sanitary sewers. The security
of these proc;essing operations is therefore in jeopardy, should the sewer
effluent be sampled and analyzed by the city during a mission period. An un
usually high BOD, a toxic constituent, high pH, or other sewer code violation
might easily lead to the discovery of the exact chemical effluent, since pol
lution literature already describes characteristics of the various wastes
discharged from other processing laboratories l ,2. By use of a 24-hour composite
sample (or a series of samples), the periodic or cycle nature of operations
could also be determined; and, with ~~ter-usage data (or flow measurements), it
would further be possible to est:linate magnitude and frequency of processing
operations.
2. Because it is generally known that operations at the contractor's
facilities are related to the manufacture and checkout of photographic equipment,
it should not be unreasonable to asst:crne that normal testing of photographic
equipment might include some limited use of processing solutions. Consequently,
a "secure" department effluent could contain photographic effluents, l)roviq.ed
the concentrations of certain key processing chemicals are lowered (or signif
icantly disproportionalized).
1, 2See References.
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Section I, Task 34
Presently, the contractor's effluents at both LP and BH fail to meet such
security requirement for continued discharge into city sewers.
3. Also, the discharge of all industrial et'fluents into the public
sewage system is now subject to regu.lation by the city Sewe"r Use Code3•
Maximum allowable standards and concentrations have been established for
both toxic and non-toxic industrial wastes which can be accepted by -the
City Sewage System. The eventual enforcement of this code will prohibit
continued
into city
DISCUSSION
4.
discharge of some types of photographic effluents now being released
sewers.
Pollution Ma~itude
a. Annual Chemical Usage _. 4 (1) An earlier report listed in tabular form the major
processing chemicals and their usage during 1968 at the contractor's BH
,facility (Table 1). More recently, a survey has been made of chemical usage
at LP for color processing (Table 2). Using literature values for chemical " * oxygen demand factors, f , for each chemical, the amount of dissolved oxygen
required by the waste constituents ioTas calculated as one estimate of pollution
magnitude.
(2) At BH, some 671:,500 Ibs. of chemicals were used and sewered
during 1968 in black-and-white processing. These chemicals had a total chemical
oxygen demand (COD) of approximately 207,000 Ibs.; or, if oxidized by bio
chemical means, a total BOD (biochemical oxygen demand) of 137,000 Ibs. The
annual average oxygen demand factor., f, was found to be 0.20 for biochemical
oxidation and 0.31 for chemical (dichromate) oxidation.
(3) For color processing at LP about 140,000 Ibs. of' chemicals
were used, or about one-fifth the amount at BH. The average COD factor is
significantly higher· (0.51) for color processing chemicals than for black-and
white, because of the greater predominance of organic chemicals used.. The
total COD amounted to over 71,000 Ibs. and a BOD total of nearly 22,000 Ibs.
3,4 See Refe~ences * Oxygen demand factor, f: "Ratio of the mass of oxygen required pel' unit
mass of the chemical.
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Approx. Solute Annual Total Solute Observed COD load
com~sition Us~e Content gOO Total Total gil} (liters) (Kg) (1))# per liter (Kg 00) (;,)#
213 49,400 10,500 21.4 41.6 2,050 8.1
45 61,000 2,750 5.6 23·9 1,460 5.8
85 138,000 11,750 24.0 18.2 2,760 10.8
35 87,200 3,030 6.2 33·5 2,920 11.5
81 105,200 8,500 17·3 24.2 2,540 10.2
221 20,700 4,550 9·3 55·1 1,220 4.8
186 41,900 7,800 16.0 293·2 12,300 48.8
4 20,800 93 0.2 0.2 5 0.0
2,166
526,966 48,973 25,255 liters Kg Kg
139,225 110,000 55,500 gal 1bs 1bs
# - Percent of Total
DO - Oxygen Demand
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20·5 . 1,010 11.6
9·2 560 6·3
11.9 1,630 18·5
24.5 2,130 24.4
7·9 830 9·4
0.6 13 0.0
62.4 2,620 29·8
0.1 3 0.0
8,796 -Kg
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Section I, Task 34
Thus, a significant percentage of each facility1s pollution comes front the
use of chemicals in the laboratory, from pre-packaged processing chemi.cals,
and miscellaneous tests which involve chemicals that do not pass through the
chemical mix rooms.
(2) In black-and-white processing during 1968, over ha.lf.
(51%) of the total chemicals used and '71% of all processing solutions prepared
were developers (Table 5). They also accounted for nearly half of the COD and
BODloads sewered (47.8 and 42.5% respectively). Fixers constituted only
16.7% of the total volume of the combined processing effluent; however, they
were responsible for most of the remaining COD. and BOD; i.e., 39.2% and 44.1%, respectively. The arrest and dye-removal baths for black-and-white processing
accounted for about 1% of the e·ffluent volume, 8% of the total salts sewered,
and about 13% of the total BOD and COD loads.
(3) Effluents from color processing are considerably d:ifferent
(Table 6). Fixers in color processing are the highest contributors of COD
and BOD (48.8 and 29.81'/0), but they constitute only 8% of the combined processing
solution volume. Stop baths also exhibit high oxygen demand. In cont:t:'ast to
black-and-white processing, each of the several color solutions contributes its
proportionate share of the total pollution. ~able 8 summarizes the magnitude
of pollution from each facility.
d. Sewer Samples
(1) Twenty-one samples of sewer effluents were collectl~d and
analyzed during selected times of missi.on and non-mission·operation. Seven
samples were taken from the LP facili t;y' and fourteen from BH. At. LP the
effluent was sampled through a clean-out valve in the basement floor, east
of Column #17 (Figure 1). At BH samples were collected from two different
locations: Manhole #1 into which only the contractor1s waste flows, and from
Manhole 1/2, which receives effluent from other ·departments in the contl'actor1s
organization.as well as the waste from Manhole #1 (See Figure 2).
(2) Preliminary analyses were made in house for pH, alk.alinity,
temperature, color, clarity, etc. Other analytical work was done elsew'here
in the contractor1s parent company according to ASTM1s "Standard Proced.ures 6l for the Examination of Water and Wastewater" •
6See References.
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Table 8
i968 Summary of BH and LP Pollution Magnitudes
Black-and·-Whi te Processing (at BH) . Chemical Usa~e:
Total Annual Usage (lbs)
Total BOD (lbs/yr) Total COD (lbs/yr)
Average BOD Factor, f (#) Average COD Factor, f (#)
Department Effluent:
Total volume (water usage) (gal/yr) Average volume (Water Usage)
(gal/day)
Average solute content (% by wt.)
Average BOD (ppm) Average COD (ppm)
Combined Processing Effluent (##)
Total annual volume (gal) Average volume (gal/day ###)
Average solute content (lbs/gal)
Average BOD (ppm) Average COD (ppm)
671,500
136,900 206,900
0.20 0.31
14,700,000
40,000
0.51
1,000 1,600
449,200 1,800
l.0
21,500 30,200
Color Processing (at LP)
139,700
21,855 71,565
0.16 0.51
25,500,000
70,000
0.061
95 310
139,225 560
0.8
15,500 44,500
(#) Pounds of oxygen required per pound of chemical
(##) Exclusive of rinse and wash water
(###) Two-hundred fifty (250) days/year
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Sampling Diagram of Plumbing Areas -- Black-and-White
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to grate (storm sewer)
Manhole #1
10
All Area 10 processing (Production and Q.C.)
All Area 11 Sanitary Drains
All Area 6 Sa.'1itary Drains
All Area 6 Processing (1 Versamat and 3 Darkrooms)
6 r-l " ~ II
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Section I, Task 34
Complete analytical data are given in the tables of Appendix A.
(3) Sampling was scheduled to be representative of "a.verage",
"best", and "worst" conditions of pollution. The average condition "'/las defined
as during the regular weekly work-day for non-mission testing, and between the
hours of 9 - 11 a.m., when the whole facility is under conditions of normal
operation. The worst condition, or greatest degree of pollution, occurs when
a mission is in house, the processing of duplicates is underway, and when
water usage from all other operations is at a minimum, i.e., nights, mornings,
or weekends. The best, or least, condition of water pollution was s-elected
as-being early in the morning during a non-mission period.
(4) At LP during a simulated mission condition, BOD, COD,
solids (total and volatile), phosphates, and alkalinity were observed to in
crease dramaticaly. However, no ~cifically defined limitation of the ex
isting sewer code is violated, other than the "slugging" or "not amenable to
treatment" clauses. Each of the above mentioned properties of the LP effluent
is certainly "unusual", and each therefore provides a potential basis for
further analysis and investigation of the effluent by agencies outside the city.
(5) The heavy metals do not vary much from maximum to minimum
conditions; nor ;Ls there.the expected increase in phenols from developer use.
Cyanides are. low in concentration, since color bleaches are no longer being
sewered, except on rare occassions. (This is because rejuvenation is in
operation at LP.) There are no toxic properties indicated by the obBerved
characteristics of these samples.
(6) The outstanding non-toxic properties of the LP effluent
at its worst condition are high BOD, COD, and phospl;1ates. A hundred··fold in
crease in phosphate concentration and in COD is clearly indicative of mission
operations or photographic testing at LP. It is also very likely that the
true BOD is much higher than the 820 ppm reported: BOD measurements on
effluents containing sanitary wastes are generally low, unless they are made
almost immediately after sampling.
(7) Samples taken from the two locations at BH show similar
properties to the processing effluents at LP: High pH, high BOD, high COD,
high solids (total and volatile), high phosphates, and high alkalinity.
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In addition, the e~~luent at BH contains signi~icant amounts o~ phenols, ~rom
developer by-products.
(8) The efffluent ~rom Manhole #1 is solely ~rom this ~acility,
and drains into Manhole 1/!2. Analysis indicates that some dilution of our
effluent occurs in Manhole 1/!2. During week days or nights this dilution ~actor
is about 1:2 or 1:3. However, when contributing areas outside the ~acility are
"down", such as on a Sunday night, our e~~luent passes through Manhole #1 and
1/!2 with little or no dilution.
5. Established Pollution Stan~
a. City Sewer Code
(1) The City Sewer Use Code3 has set speci~ic limitations on
only a ~ew o~ the common polluta.nts or deleterious properties o~ industrial
waste. Moreover, to date this code has not been strictly policed or enforced;
it has there~ore been possible to utilize the City's sewers and treai~ent
center ~or photographic processing e~~luents. A strict interpretation o~ the
code,'however, might prohibit the continued sewering o~ e~fluent by present
disposal practices.
(2) Under the terms o~ the City Sewer Use Code, the clischarge
of any water, sewage, or industrial ,vaste "which in concentration o~ any given
constituent or in volume of flow, exceeds for any period o~ duration longer
than five (5) minutes more than ~ive (5) times the average twenty-foux (24)
hour concentration or ~lows during normal operation," is termed a "Slug".
Slugs are prohibi ted i~, "in the opinion of the Commissioner o~" Public Works,"
they are "likely to harm" or rrhave a.n adverse e~fect" upon the sewer system
or treatment process.
(3) Since photographic effluents change drastically in volume
and in properties (more than a ~actor of ~ive from the average values*) the
term "slugging" is applicable to our ef~luent. At BH, samples taken from
Manhole 1/!2 indicate:
3See Re~erences. * Appendix P: Tables.,
(a)
(b)
(c)
COD values of 150 ppm (average) and 17,200 PIJm (maximum) •
Total solids, from 380 ppm '(average) and 4,000 ppm (maximum) •
Total suspended solidS, 10 ppm (average) and 100 ppm (maximum). ,
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Iron, alkalinity, and phosphates also vary considerably (more than five times
the average concentration), but these properties are not presently detrimental
to sewage treatment at crurrent volumes and concentrations.
(4) At LP, "slugging" conditions exist, again attributable
to COD, BOD total and volatile solids, phosphate concentration, and alkalinity.
Each o:f these effluent characteristics (except alkalinity), are serious
changes in properties and should reeeive corrective abatement measUJ:'es. If
security were not also involved, storage facilities for the LP insta.llation
would probably be adequate to prevent "slugging" and provide an "acceptable"
effluent.
(5) The pH of the effluent is a likely sewer use code violation
at both installations, as the alkalinity is above 10.0 when developer use is
at a maximum*.
(6) Another possible sewer code violation could involve
sewering "toxic" materials or wastes not "amenable" to waste treatment. Under
this ·category heavy metals such as chromium, zinc, copper, lead, tin, and
nickel are often restricted, as well as toxic materials, such as cyanides.
Our effluent contains chromium ion from potassium dichromate - sulfruoic acid
cleaning solution (Kodak. System Cleaner) and organic phosphorous com])ounds,
i.e, the bactericide solution, Dowicide G. An established limit has been set
for cyanides (2 mg/l as CN). However, most sewer codes·7 have specif:i.c limi t
ations on some or all of the toxic heavy metals.
(7) It '.shouJ.d be noted, however, that at present there are
no actual, defined violations of the C:Lty Sewer Use Code at either fa.cility,
with the possible exception of pH. Adjustment in pH, if found to be necessary
to comply with the ~ode, can easily be made by storage and treatment with an
inexpensive aCid, such as sulfuric aeid. Storage tanks would also reduce
any potential problems due to slugging.
* The alkaline effluent is generally diluted with a more acidic waste.
7
However, during mission periods over weekends, when other contributing· areas outside the facility are "down", the combined effluent to the sewer exceeds the pH limit of 10.0.
See References.
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(8) As more is learned by the city about the effect of
specific industrial wastes on the performance of its treatment center, no
doubt additional restrictions will be added and enforced. Current research
literature indicates that some photographie effluents are not amenable to
city primary and secondary treatment plants 8•
b. Rules, Classificationz and Standards for the State
(1) It is the declared "public policy of the state to maintain
reasonable standards of purity of the waters of the state consistent with
public health, and enjoyment thereof, II including the "propagation and pro
tection of fish and wild life •••• 9 II
(2) In accordance with the above policy, and under the
authority of the state public health law, rules and regulations on the dis
charge of any waste effluent have been adopted by the State I s water l)ollution
Control Board. The established rules and standards are based upon the
principle that an effluent being discharged into any natural body of water
must not so pollute the receiving body that its classified best usage will
be impaired.
(3) Water resources vrithin the state are therefore classified
according to their "best usage," and quality standards have been established
for twelve water classes9 , Untreated photographic wastes, such as from our
facilities, could be disposed only in receiving bodies having the lowest
ratings, i.e, rated as Class E or.F (for sewage, industrial wastes, or trans
portation only).
c. Federal Attitude and Standards
(1) Five Federal laws containing provisions related to water
pollution have been enacted by the Congress. Two of these are primar:i.ly
concerned with preventing damage to shipping. The Public Health Service
Act of 1912 gave specific authority for the PHS (Public Health Service) to
conduct investigations and research on the pollution of streams and lE~es
by sewage and other causes. The Water Pollution Control Act of 1948
(P.L. 845, 80th Congress) authorized expanded activities and responsibi1i ty
of the federal government; added the principles of state-federal cooperative
program development, limited Federal enforcement, but gave financial aid.
8 9 , See References.
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Section I, Ta.sk 34
In 1961 the water-pollution-control program became administered directly by
the Secretary. of the Department of Health, Education, and Welfare and a
previous restriction limiting federal enforcement to interstate waters was
amended to include interstate or navigable waters.
(2) The federal position in regard to quality is clearly
one of concern, but Congress recognizes that primary responsibility in the
field of water pollution rests with the states. The federal role is to
provide technical services and financial aid to states, agenCies, and
municipalities. NO national standards or regulations have been developed
for control of wastes into surface waterslO
•
d. Sunnnary. The pollution control standards which most directly
apply to the discharge of photographic effluents by this contractor are those
established by the city in its Sewer Use Code. Standards accepted to meet
the security requirement (See next Section) will more than adequately comply
with the established city sewer usage code.
6. Acce~table Security Controb
a. Control Measures. The maintenance of operational sectITity
and prevention of a breach of security via waste discharge necessitates
several pollution-control steps for our department: (1) Strict maintenance
of an acceptable waste effluent, which will reduce or eliminate the need
for a detailed analysis of our effluent by an outside agency. (2) Keeping
photographic flags at a minimum: constituents or characteristics indicative
of processing, (3) Disproportionalizing so that the true magnitude of' such
operations will not be revealed, (4) Disguising the cycle character~stics
of our industrial waste.
b. Acceptable Department Waste Characteristi9s
(1) Continued use of the sewer means that the city will
eventually collect and analyze samples of waste water containing effluents
from this facility. It is therefore of prime" importance that our discharge
be an "acceptable" industrial waste in every way to the city.
10 See Reference.
A-21
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Section I, Task 34
(2) Industrial waste-water characteristics that are of
present interest to the city are listed in Table 9. Botll toxic and non
toxic limitations are specified.
c. Toxic Standards. The specific toxic limitations imposed by
the city code that are relevant to our effluent are for cyanide and heavy
metals. Only 2 mg/l (or ppm) of both simple and complex cyanides (as CN)
are allowed. Also limited are the heavy metals, such as chromium, zinc,
copper, lead, tin, and nickel. Their content should not exceed 10 PJJ.m in
solution or more than 30 ppm in total. These toxiS standards mean that
color bleaches and acid-dichromate solutions must be eliminated from our
effluents.
d. Non-Toxic Standards
(1) Non-toxic characteristics acceptable as waste for the
city sewer include the following specific limitations:
Table 10
Non-toxic Limitations for Wastes Accepted by City
Flammables: None
Temperature of effluent:
pH (at 70°F.)
Oils and grease
Not over l50°F.
Between 5.5 and 10.0
Not over 100 ppm
(2) In addition, under the restrictions, "no unusual" or , ,
"excessive" conditions, our effluent should not violate the following
suggested limitations:
Table 11
Suggested Effluent Limitations
BOD:
COD:
Color:
Solids (Total):
Solids (Suspended):
Total Nitrogen:
Ammonia Nitrogen (NH3
):
A-22
Not over 300 ppm
Not over 750 ppm
Pale colors only
Not over
Not over
Not over
Not over
1000 ppm
400 ppm
50 ppm } 25 ppm
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Table 9
Industrial Waste Characteristics and Quantities
At BH, Manhcle #1 1-At BH, Manbole #2 ---I At LP
Average ~ ~ Average ~ ~ Average ~ 40,000 38,400 111,000 70,000 6i,000
Total Nitrogen (N) NLE Not Measured Not Measured Not Measured 50 Ammonia (NH ) NLE Not Measl.lxed Not Measured Not Measured 25 Misc. solid~ or viscous (1) None None None None None
No specific limit given; but no "unusual" condition allowed.
~:
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~.~~ (5)
(6) (7) (8 ) (9)
considered toxic and therefore, not "amenable" to treatment and restricted. Suggested limits set by other Sewerage Codes (Ref. 7,11). Any radioactive waste must meet applicable State or Federal regulations. Total of chxomium, zinc, cadmium, copper, lead, tin, nickel, silver -- not to
exceed 10 ppm in solution and 30 ppm in total (Ref. 7). All values given in ppm, unless stated otherwise. * Based on analYSis of samples from manhole #2. NLE - No limit established by City Sewer Code. None - Means none allowed.
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Section I, Task 34
CONCLUSIONS
7. Safe levels of the more significant characteristics requiring
control for pollution abatement and. security are:
a.
b.
Non-toxic Characteristics
(1) COD of 750 ppm
(2) BOD of 300 ppm
(3) Phosphate of 15 ppm
(4) Total solid content of 2000 ppm
Toxic Characteristics*
(1) Chromium ion (mainly from cleaning solutions) - complete
removal or prohibitiop of discharge in the effluent.
(2) Cyanide (or ferrous and ferric salts) - complete removal
or prohibition of discharge in the effluent.
8. In addition to the above, cyclic clues to the nature of our operations
should be removed by minimizing or reducing "slugging", or periodic discharge
of high and low concentration chemical effluent. Among the clues of chief
concern are the concentrations of phenols, halides, acetates, thiosulfates
and sufites.
9. Adherence to the needs specified by paragraphs 7 and 8 above
will specify the choices of treatment to satisfy both pollution abatement
and security. Also, it appears that a single treatment or series of treat
m,ents is feasible to achieve these objectives.
10. Of local, state and federal regulations, only the local city
Sewer Use Code is strictly applicable as a guide for establishing pollution
standards. At present, this guide is broadly worded, not strictly enforced,
and otherwise unsuitable to define our total needs for pollution control.
11. While the major concern is the abatement of pollution from mission
processing operations, the total problep1 must embrace photographic support
activities, such as laboratory testing and other use of chemicals not used
directly for mission processing. These additional sources make up 25 to 3Cf/o
* A contractor's study was completed under Phase I, Section II ~f this task 14 to find a connnon bleach and a method to regenerate and reuse color bleaches. As a consequence of this study, lore have discontinued zinc precipitation of cyanides in spent bleaches and sE~ering of the toxic solids. Also, we have taken steps to eliminate or minimize the acid dichromate cleaning solution previously used to clean equipment at the end of each mission.
14 See References.
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Section I, Task 34
of the pollution contribution from this facility.
12. To maintain a more accurate concept of the type and magnitude of
pollutants, !!l processing, testing and other chemicals should be recorded.
13. We need an automatic sampling device to further improve sampling
accuracy and better assure that samples are representative of critical
periods in the operation cycle. Such devices are commercially available,
and once installed would have the aClditional advantage of more economical
sampling activity.
A-29
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Section I, Task 34
RECOMMENDATIONS
14. Adopt and maintain standards of the type summarized in paragraphs
7 and 8, and as given more completel:f in Table 13 of the text, to adequately
achieve pollution abatement and sec~~ity.
15. Record all chemicals, chemical mixes and other preparations used
by the contractor to facilitate adequate monitoring.
16. Purchase a connnercially available twenty-four hour sampling device
for use in future effluent sampling and analysis. . '.
A-30
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Section I, Task 34
REFERENCES
1. Mohahrao, G. J. et aI, "Photo-Film Industry Wastes: Pollution Effects and Abatement," Central Public 'Health Engineering Research Institute, Nagpur, India, 1965.
2. Eustance, n., "Treating Photo-Industry Process Waste," Industrial Water and Wastes, Vol. 5, p 5, 1969.
3. Sewer Use Code, Code of the City of Rochester, Chapter 97, 196.:3.
4. FINAL REPORT, "Study of Pollution Contribution From Processing Activities," Contract EG-400, Task 34, Section VII, 3 March 1969.
5. From unpublished data of a contractor's six-month survey during 1968 of water usage rates at both installations.
6. "Standard Methods for the Examination of Water and Wastewater," American Public Health Assn. , Inc., N.Y. 12;th Edition, 1965.
7. James, G. V., Water Treatmen!, Darien Press, Ltd. Edinburgh, p 193, 1966.
8. Mohanrao, op. cit., pp 190-198.
9. "Rules and Classifications and Standards of Quality and Purity for Waters of New York State," N. 1. Public Health Law, Chapter 490, Article 12. (Adopted by the N.Y. Water Pollution Control Board)
10. McKee, Jack Edward, and Wolf, Harold w., Water Quality Criteri<~, State Water Quality Control Board, Sacramento, California, No. 3A., pp 31-32, 1963:
11. Kemp, Lowell E., et aI, Biology of Water Pollution, U. S. Department of the Interior, Federal Water Pollution Control Administration, pp 150-152, 1967.
12. Nimerow, Nelson Leonard, Theories and Practices of Industrial Haste Treatment, Addison-Wesley Publishing Co., Reading, Mass., pp Ih3-149, 1963.
13. Standard Methods, op. cit. pp 515.
14. Pollution Studies, Phase I, Seetion II, "Elimination of Presently Defined Toxic Chemicals," Common Bleach Studies, 31 March 1969.
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Section I, Ta,sk 34
APPEND IX AI
Industrial Waste Characteristics
Tables i-I and A-2 list separately the characteristics of the effluents from each of the contractor's two facilities, BH and LP.
A-·32
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Industrial Waste Characteristics of Samples from BH
Other Note s: All samples taken fran clean-out valve near Column 17 (Figure 2). All values are in ppn (parts per million), unless stated otherwise. #: ;Alkalinity/acidity as PJII! CaC0
3•
Dashes mean data not available. means less than.
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APPENDIX B
This appendix contains a reproduction of FINAL REPORT on
"Study of Pollution Contribution from Processing Activities,"
Contract EK-1904, Task 34, Section VII, 3 March 1969. This
report was published 21 April 1969.
B-1
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TABLE OF' CONTENTS
Sffiv1MA.RY
SUBJECT
TASK (from Study Plan)
DISCUSSION
l. Chemical Usage
2. BOD/COD Load
3. Processing Solution Volumes
4. Water Usage and Dilution Ratio
5. Systems
6. Ammonium
7. Dowicide
CONCLUSIONS
8.
RECOMMENDATIONS
REFERENCES
Cleaner
Salts
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Section VII, Task 34
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5
5
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5
5
6
8
8
11
11
13
13
14
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Section VII, Task 34
LIST OF TABLES
Title
Chemical Usage and Pollution at Bridgehead 7
Processing Solution Volumes - 1968
Water Usage and Dilution Ratios
B-3
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Section VII, Task 34
SUMMARY
A survey was made of the types and amounts of photographic chemicals
used as well as department water-usage rates and volume::> for black-and-white
mission and testing activity at Bridgehead during 1968. From these data,
the pollution problem has been characterized.
Developers constituted 71. CP/o of the volume of processing effluent at
Bridgehead -- exclusive of rinse waters. Fixers and arrest baths accounted
for 16.5% and 11. 5%, respectively*. Under typical mission conditions,
about 2300 gallons of processing solutions are prepared, used, and sewered
each 24-hour day. The worst condition observed in 1968 was for a 13-·day
period when an average of 2500 gallons were used each day.
Department water-usage rates vary from 1600 to 4600 gallons per hour;
the peak rate is observed on the "A" shift during testing activities be
tween missions. Water usage rates constitute a reliable indication of
mission activities, however, only when observed hour-by-hour. About 14.7
million gallons of water was used by the departmeBt in- 1968. The dilution
factor (ratio of water volume to processing effluent) averaged about 33
and ranged from 13 to 55.
Recommendations are:
a. Reduce and/or control the discharge of "tQxic" chromic:
acid cleaner solution.
b. Study arrest replenisher rates or water cut-off (without
use of arrest bath) to further reduce pollution.
* The other 1. CP/o "as made up of miscellaneous chemical solutions.
B--4
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SUBJECT: Study of Pollution Contribution From Processing Activities
TASK
A. Determine Processing Solution Usage For:
1. Non-mission processing.
2. Machine checkout.
3. Pre-mission checkout.
Section VII, Task Ji.!
B. Determine Cleaning Solution Usage for Cleaning Processors. Consideration
will be given to the concentration and possible effects of the chromium ion
contained in waste cleaning solutions.
C.
1. Pre-mission.
2. Post-mission.
3. other cleaning.
Study Pollution Contribution From Versamats and Other Small Processors In House
DISCUSSION
1. Chemical Usage
a. Earlier pollution reportsl
,2 list the processing chemicals
used and machine replenisher rates for 1956 at Bridgehe8.d. More recent data
for black-and-white processing were obtained in a survey of make-up E:heets
from the chemical mix room. These data, shown in Table 1, represent actual
chemicals used and s'ewered for testing and pruduct-ien during 1968. b. Over 335 tons of 19 different ch~nicals were used at Bridge
head during 1968. This tonnage is a significaIlt reduction from the quantity
used two years earlier (1966 usage was nearly 600 tons), when pollution
abatement began with a study and subsequent read,j ustmeBt C)f replenisher rates.
As the annual water. usage for 1968 was 14.7 million gallons, the solids content
in the department's effluent for that year avera.ge 0.L,·6 lb. per gallon
(55,000 ppm or 5.5% by weight).
2. BOD/COD Load
a. Currently, the degree of water pollution is generally de-
termined by the quantity of oxygen required to ()xic1L:,i, r:onsti tuents of the
effluent. In a treatment center this oxygen demaucl (,:0) may be satisfied
either chemically as in chlorination, or biochemically, as by the bacteria in
an activated sludge system.· The degree of oxidation iE: not usually the same.
1 2 , See References.
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Section VII, Task 34
The Chemical Oxygen Demand (COD) of a pollutant is generally greater than the
Biochemical Oxygen Demand (BOD). Because most large treatment centers use an
activated-sludge process, the BOD load of an effluent is generally involve~.
Unfortunately, the analytical procedure for determining BOD usually requires
a minimum of five days so that, whenever possible, pollution is evaluated by
means of COD tests. Analytical procedure for COD testing requires only one
to two hours.
b. In Table 1, the BOD and COD factors (f) are given for each of
the chemicals used. Multiplying the annual usage by this fa.ctor gives the
COD load or amount of pollution. During 1966 and 1968, the oxygen demand for
processing was 0.31 lb. of chemical oxygen (or 0.20 lb. of biochemical 0xygen)
for every pound of chemicals used. The amount of pollution in 1968 w'as about
35% lower than for 1966. c. Seventy-three to eighty-five percent of the pollution load in
( 0 I (3 - NotE: Values in parentheses ar2 estimates. td !II ::s
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Section VII, Task 34
b. The processing solutions required for a typical black-and-white
mission in 1968 are given in Table 2, Part B. Developers account for over 7CP!o
and fixers 19% of the combined processing effluents, which average 2300 gallon:::
per day for a 15-day period .
c. In 1969, when the rejuvenation and re-use of hypo is :in full
operation, developers should constitute 84% of. the processing solutions
prepared for each mission. HYPo and arrest combined, in about equal quan
ti ties, will account for only 15%. The average daily volume of processint~
solutions (exclusive of rinse water) should drop slightly to about 2000
gallons per day (85 gallons per hour) during mission work.
d. The vwrst condition observed in 1968 was for a 13-day mission
during which some 120,750 liters of processing solutions were prepared, used,
and sewered, giving an average of 2500 gallons/day. The worst condition in
.1969 should. not exceed 3000 gallons of combined processing effluents.
4. Water Usage and Dilution Ratio
a. Water meter readings 1-rere taken twice daily throughout 1968.
Total department usage was 14.7 million gallons for processing, testing,
mix room, etc. An analysis was made of the data to determine how much usaf:,e
rates varied during the day, night, or over the weekend for both mission and
non-mission intervals. Significant differences in usage rates were observed.
as noted in Table 3.
b. The maximum rate occurs on non-mission days when there is
cqnsiderable in-house testing. From 4 PM to 8 AM daily and over weekends,
water usage is 1600 gph for non-mission periods and 2250 gph for mission
periods, an increase of 650 gph which is clearly discernable. If only daily
(24 hour interval) records are taken" the rates would be 2730 and 3120 gpb , respectively for non-mission and mission days. Thus, water usage rates a:r-::
v.alid indicators of mission activities if hourly checks are made on nightc;,
holidays, or weekends .. If only daily, weekly, or monthly data are obtainEd,
reliable correlation with missi0n activities would probably not be possible.
5. Systems Cleaner
a. During 1968, 3000 Ibs. of Kodak Developer ,systems Cleaner
was used within the department.
acid (NH2
S03
H) and 35% potassium
romate contains 35.35% chromium,
This product is approximately 65% sulfamic
dichromate (K{r2
07
). As potassium dich
some 370 Ibs. of chromium was sewered in
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Table 2
Processing Solution Volumes - 1968
I Part A: Annual Usage I Approx.
~ajor Cone. Constituents sh. 11 tersZYI..'
l. Deve lopers: Misc. organic & 4.0-120 inorg. chemicals (87 av) 1,21/,000
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